MECHANISMS OF HETEROGENEOUS OXIDATIONS AT MODEL AEROSOL INTERFACES BY OZONE AND HYDROXYL RADICALS

Atmospheric aerosols play an important role in climate by scattering and absorbing radiation and by serving as cloud condensation nuclei. An aerosol’s optical or nucleation properties are driven by its chemical composition. Chemical aging of aerosols by atmospheric oxidants, such as ozone, alters the physiochemical properties of aerosol to become more hygroscopic, light absorbing, and viscous during transport. However the mechanism of these transformations is poorly understood. While ozone is a protective and beneficial atmospheric gas in the stratosphere, it is a potent greenhouse gas in the troposphere that traps heat near the Earth’s surface. It also impacts human heath by irritating the respiratory tract and exacerbating cardiovascular diseases. Additionally, ozone can alter the ecosystem through oxidizing plant foliage which can lead to deforestation and crop losses as well. Both gases and aerosols in the troposphere can react with ozone directly and indirectly with hydroxyl radicals. While daytime aging is thought to be primarily driven by photochemical processes and hydroxyl radicals, ozone is thought to be a key player in nighttime or dark aging processes that can alter the physicochemical properties of aerosols. Measured concentrations of trace gases and aged aerosol components in the field are higher than values predicted based on laboratory studies and computer simulations. Consequently, new experimental approaches are needed to narrow the gaps between observations and mechanistic understandings. In this dissertation, a plume of microdroplets was generated by pneumatically assisted aerosolization and then exposed to a flow of ozone before entering a mass spectrometer. This surface-specific technique allowed for the real-time analysis of reaction products and intermediates at the air-water interface. This work explores the in situ oxidation of iodide, a component of sea spray aerosols, by 0.05 – 13.00 ppmv ozone to explore how heterogeneous oxidation could enhance the production of reactive iodide species. Methods to study the reaction channels and intermediates were also established to not only determine a mechanism of iodide oxidation by ozone, but to enable the study of more complex systems. The developed approach was then applied to examine the oxidation of catechol and its substituted cousins, a family of compounds selected to model biomass burning and combustion emissions, at the air-water interface. While literature suggested that the primary mechanism of catechol oxidation by ozone would be the cleavage of the C1-C2 bond, it was determined that this was only a minor pathway. An indirect oxidation channel dominated heterogeneous processes at the air-water interface, giving rise to hydroxyl and semiquinone radicals that recombine to produce polyhydroxylated aromatics and quinones. This new mechanism of aging represents an overlooked channel by which brown, light-absorbing carbon aerosols are produced in the atmosphere. In addition, the work investigates how reactions on solid particulate aerosols proceed under variable relative humidity. Thin films were developed alongside a novel flow-through reactor to study of how aerosols are transformed by ozone and hydroxyl radicals when exposed to 50 ppbv - 800 ppmv of ozone. This system was employed to probe how catechol reacts with ozone under variable relative humidity. Further work was undertaken to model the adsorption process at the air-solid interface under variable humidity, permitting the estimation of the reactive uptake of ozone by the film at concentrations (50-200 ppbv) seen in rural and urban areas. Together, these results provide an increased understanding of how heterogeneous oxidation of aerosols contributes to aerosol aging processes as well as free radical production in the troposphere

Interfacial Oxidative Oligomerization of Catechol.

The heterogeneous reaction between thin films of catechol exposed to O3(g) creates hydroxyl radicals (HO•) in situ, which in turn generate semiquinone radical intermediates in the path to form heavier polyhydroxylated biphenyl, terphenyl, and triphenylene products. Herein, the alteration of catechol aromatic surfaces and their chemical composition are studied during the heterogeneous oxidation of catechol films by O3(g) molar ratios ≥ 230 ppbv at variable relative humidity levels (0% ≤ RH ≤ 90%). Fourier transform infrared micro-spectroscopy, atomic force microscopy, electrospray ionization mass spectrometry, and reverse-phase liquid chromatography with UV–visible and mass spectrometry detection provide new physical insights into understanding the surface reaction. A Langmuir–Hinshelwood mechanism is accounted to report reaction rates, half-lives, and reactive uptake coefficients for the system under variable relative humidity levels. The reactions reported explain how the oligomerization of polyphenols proceeds at interfaces to contribute to the formation of brown organic carbon in atmospheric aerosols

Data Generated during the 2018 LAPSE-RATE Campaign: An Introduction and Overview

Unmanned aircraft systems (UASs) offer innovative capabilities for providing new perspectives on the atmosphere, and therefore atmospheric scientists are rapidly expanding their use, particularly for studying the planetary boundary layer. In support of this expansion, from 14 to 20 July 2018 the International Society for Atmospheric Research using Remotely piloted Aircraft (ISARRA) hosted a community flight week, dubbed the Lower Atmospheric Profiling Studies at Elevation – a Remotely-piloted Aircraft Team Experiment (LAPSE-RATE; de Boer et al., 2020a). This field campaign spanned a 1-week deployment to Colorado\u27s San Luis Valley, involving over 100 students, scientists, engineers, pilots, and outreach coordinators. These groups conducted intensive field operations using unmanned aircraft and ground-based assets to develop comprehensive datasets spanning a variety of scientific objectives, including a total of nearly 1300 research flights totaling over 250 flight hours. This article introduces this campaign and lays the groundwork for a special issue on the LAPSE-RATE project. The remainder of the special issue provides detailed overviews of the datasets collected and the platforms used to collect them. All of the datasets covered by this special issue have been uploaded to a LAPSE-RATE community set up at the Zenodo data archive (https://zenodo.org/communities/lapse-rate/, last access: 3 December 2020)

Intercomparison of Small Unmanned Aircraft System (sUAS) Measurements for Atmospheric Science During the LAPSE-RATE Campaign

Small unmanned aircraft systems (sUAS) are rapidly transforming atmospheric research. With the advancement of the development and application of these systems, improving knowledge of best practices for accurate measurement is critical for achieving scientific goals. We present results from an intercomparison of atmospheric measurement data from the Lower Atmospheric Process Studies at Elevation—a Remotely piloted Aircraft Team Experiment (LAPSE-RATE) field campaign. We evaluate a total of 38 individual sUAS with 23 unique sensor and platform configurations using a meteorological tower for reference measurements. We assess precision, bias, and time response of sUAS measurements of temperature, humidity, pressure, wind speed, and wind direction. Most sUAS measurements show broad agreement with the reference, particularly temperature and wind speed, with mean value differences of 1.6 ± 2.6 °C and 0.22 ± 0.59 m/s for all sUAS, respectively. sUAS platform and sensor configurations were found to contribute significantly to measurement accuracy. Sensor configurations, which included proper aspiration and radiation shielding of sensors, were found to provide the most accurate thermodynamic measurements (temperature and relative humidity), whereas sonic anemometers on multirotor platforms provided the most accurate wind measurements (horizontal speed and direction). We contribute both a characterization and assessment of sUAS for measuring atmospheric parameters, and identify important challenges and opportunities for improving scientific measurements with sUAS

Ionization of He, Ne, Ar, Kr, and Xe by proton impact: Single differential distributions in energy and angles

In this paper we report energy and angular distributions of electrons emitted in collisions of protons with neon- F− ,Ne0 ,Na+, argon- Cl− ,Ar0 ,K+, krypton- Br− ,Kr0 ,Rb+, and xenon- I − ,Xe0 isoelectronic series for high and intermediate impact energies. Calculations were performed within the continuum distorted waveeikonal initial-state method using an angular expansion in spherical harmonics and a numerical evaluation of the radial functions corresponding to both: the initial bound and the final continuum states in the same central potential. The first Born approximation was calculated on equal footing. The shellwise local plasma approximation was also calculated when possible. A complete and exhaustive comparison with the available experimental data is carried out. We have spanned almost all the published experiments in our range of interest. Successes and failures of the different theoretical methods are pointed out. Possible signatures of manyelectron effects are noticed.Fil: Miraglia, Jorge Esteban. Consejo Nacional de Investigaciónes Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Astronomía y Física del Espacio. - Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Astronomía y Física del Espacio; Argentin

Interfacial Oxidative Oligomerization of Catechol

The heterogeneous reaction between thin films of catechol exposed to O3(g) creates hydroxyl radicals (HO•) in situ, which in turn generate semiquinone radical intermediates in the path to form heavier polyhydroxylated biphenyl, terphenyl, and triphenylene products. Herein, the alteration of catechol aromatic surfaces and their chemical composition are studied during the heterogeneous oxidation of catechol films by O3(g) molar ratios ≥ 230 ppbv at variable relative humidity levels (0% ≤ RH ≤ 90%). Fourier transform infrared micro-spectroscopy, atomic force microscopy, electrospray ionization mass spectrometry, and reverse-phase liquid chromatography with UV–visible and mass spectrometry detection provide new physical insights into understanding the surface reaction. A Langmuir–Hinshelwood mechanism is accounted to report reaction rates, half-lives, and reactive uptake coefficients for the system under variable relative humidity levels. The reactions reported explain how the oligomerization of polyphenols proceeds at interfaces to contribute to the formation of brown organic carbon in atmospheric aerosols

Environmental and Sensor Integration Influences on Temperature Measurements by Rotary-Wing Unmanned Aircraft Systems

Obtaining thermodynamic measurements using rotary-wing unmanned aircraft systems (rwUAS) requires several considerations for mitigating biases from the aircraft and its environment. In this study, we focus on how the method of temperature sensor integration can impact the quality of its measurements. To minimize non-environmental heat sources and prevent any contamination coming from the rwUAS body, two configurations with different sensor placements are proposed for comparison. The first configuration consists of a custom quadcopter with temperature and humidity sensors placed below the propellers for aspiration. The second configuration incorporates the same quadcopter design with sensors instead shielded inside of an L-duct and aspirated by a ducted fan. Additionally, an autopilot algorithm was developed for these platforms to face them into the wind during flight for kinematic wind estimations. This study will utilize in situ rwUAS observations validated against tower-mounted reference instruments to examine how measurements are influenced both by the different configurations as well as the ambient environment. Results indicate that both methods of integration are valid but the below-propeller configuration is more susceptible to errors from solar radiation and heat from the body of the rwUAS

Merging Unmanned Aerial Systems (UAS) Imagery and Echo Soundings with an Adaptive Sampling Technique for Bathymetric Surveys

Bathymetric surveying to gather information about depths and underwater terrain is increasingly important to the sciences of hydrology and geomorphology. Submerged terrain change detection, water level, and reservoir storage monitoring demand extensive bathymetric data. Despite often being scarce or unavailable, this information is fundamental to hydrodynamic modeling for imposing boundary conditions and building computational domains. In this manuscript, a novel, low-cost, rapid, and accurate method is developed to measure submerged topography, as an alternative to conventional approaches that require significant economic investments and human power. The method integrates two types of Unmanned Aerial Systems (UAS) sampling techniques. The first couples a small UAS (sUAS) to an echosounder attached to a miniaturized boat for surveying submerged topography in deeper water within the range of accuracy. The second uses Structure from Motion (SfM) photogrammetry to cover shallower water areas no detected by the echosounder where the bed is visible from the sUAS. The refraction of light passing through air–water interface is considered for improving the bathymetric results. A zonal adaptive sampling algorithm is developed and applied to the echosounder data to densify measurements where the standard deviation of clustered points is high. This method is tested at a small reservoir in the U.S. southern plains. Ground Control Points (GCPs) and checkpoints surveyed with a total station are used for properly georeferencing of the SfM photogrammetry and assessment of the UAS imagery accuracy. An independent validation procedure providing a number of skill and error metrics is conducted using ground-truth data collected with a leveling rod at co-located reservoir points. Assessment of the results shows a strong correlation between the echosounder, SfM measurements and the field observations. The final product is a hybrid bathymetric survey resulting from the merging of SfM photogrammetry and echosoundings within an adaptive sampling framework

Moving towards a Network of Autonomous UAS Atmospheric Profiling Stations for Observations in the Earth’s Lower Atmosphere: The 3D Mesonet Concept

The deployment of small unmanned aircraft systems (UAS) to collect routine in situ vertical profiles of the thermodynamic and kinematic state of the atmosphere in conjunction with other weather observations could significantly improve weather forecasting skill and resolution. High-resolution vertical measurements of pressure, temperature, humidity, wind speed and wind direction are critical to the understanding of atmospheric boundary layer processes integral to air–surface (land, ocean and sea ice) exchanges of energy, momentum, and moisture; how these are affected by climate variability; and how they impact weather forecasts and air quality simulations. We explore the potential value of collecting coordinated atmospheric profiles at fixed surface observing sites at designated times using instrumented UAS. We refer to such a network of autonomous weather UAS designed for atmospheric profiling and capable of operating in most weather conditions as a 3D Mesonet. We outline some of the fundamental and high-impact science questions and sampling needs driving the development of the 3D Mesonet and offer an overview of the general concept of operations. Preliminary measurements from profiling UAS are presented and we discuss how measurements from an operational network could be realized to better characterize the atmospheric boundary layer, improve weather forecasts, and help to identify threats of severe weather

The Innovative Strategies for Observations in the Arctic Atmospheric Boundary Layer Project (ISOBAR) — Unique fine-scale observations under stable and very stable conditions

The Innovative Strategies for Observations in the Arctic Atmospheric Boundary Layer Program (ISOBAR) is a research project investigating stable atmospheric boundary layer (SBL) processes, whose representation still poses significant challenges in state-of-the-art numerical weather prediction (NWP) models. In ISOBAR ground-based flux and profile observations are combined with boundary-layer remote sensing methods and the extensive usage of different unmanned aircraft systems (UAS). During February 2017 and 2018 we carried out two major field campaigns over the sea ice of the northern Baltic Sea, close to the Finnish island of Hailuoto at 65 °N. In total 14 intensive observational periods (IOPs) resulted in extensive SBL datasets with unprecedented spatiotemporal resolution, which will form the basis for various numerical modeling experiments. First results from the campaigns indicate numerous very stable boundary layer (VSBL) cases, characterized by strong stratification, weak winds, and clear skies, and give detailed insight in the temporal evolution and vertical structure of the entire SBL. The SBL is subject to rapid changes in its vertical structure, responding to a variety of different processes. In particular, we study cases involving a shear instability associated with a low-level jet, a rapid strong cooling event observed a few meters above ground, and a strong wave-breaking event that triggers intensive near-surface turbulence. Furthermore, we use observations from one IOP to validate three different atmospheric models. The unique fine-scale observations resulting from the ISOBAR observational approach will aid future research activities, focusing on a better understanding of the SBL and its implementation in numerical models