Development of 2-D-MAX-DOAS and Retrievals of Trace Gases and Aerosols Optical Properties

Air pollution is a major problem worldwide that adversely affects human health, impacts ecosystems and climate. In the atmosphere, there are hundreds of important compounds participating in complex atmospheric reactions linked to air quality and climate. Aerosols are relevant because they modify the radiation balance, affect clouds, and thus Earth albedo. The amount of aerosol is often characterized by the vertical integral through the entire height of the atmosphere of the logarithm fraction of incident light that is extinguished called Aerosol Optical Depth (AOD). The AOD at 550 nm (AOD550) over land is ~ 0.19 (multiannual global mean), and that over oceans is 0.13. About 43 % of the Earth surface shows AOD550 smaller than 0.1. There is a need for measurement techniques that are optimized to measure aerosol optical properties under low AOD conditions, sample spatial scales that resemble satellite ground-pixels and atmospheric models, and help integrate remote sensing and in-situ observations to obtain optical closure on the effects of aerosols and trace gases in our changing environment. In this work, I present the recent development of the University of Colorado two dimensional (2-D) Multi-AXis Differential Optical Absorption Spectroscopy (2-D-MAX-DOAS) instrument to measure the azimuth and altitude distribution of trace gases and aerosol optical properties simultaneously with a single instrument. The instrument measures solar scattered light from any direction in the sky, including direct sun light in the hyper spectral domain. In Chapter 2, I describe the capabilities of 2-D measurements in the context of retrievals of azimuth distributions of nitrogen dioxide (NO2), formaldehyde (HCHO), and glyoxal (CHOCHO), which are precursors for tropospheric O3 and aerosols. The measurements were carried out during the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) campaign in Mainz, Germany and show the ability to bridge spatial scales to satellites and atmospheric models. Chapter 3 presents an innovative retrieval approach to measure AOD430 and the aerosol phase function parameter, g, without the need for absolute radiance calibration; the retrieval is based on solar azimuth distributions of the Raman Scattering Probability (RSP), the near-absolute Rotational Raman Scattering (RRS) intensity, during the Department of Energy Two Column Aerosol Project (TCAP) at Cape Cod, MA. Furthermore, the TCAP field campaign provides a unique dataset to evaluate innovative retrieval algorithms and perform radiation closure studies. In Chapters 4 I describe the effect of persistent elevated aerosol layers on the apparent absorption of the collision induced absorption of oxygen (O2-O2, or O4) as seen by the ground based 2-D-MAX-DOAS. Chapter 5 discusses the effect of chemical composition of aerosols for optical closure of aerosol extinction as characterized by ground based (2-D-MAX-DOAS) and airborne remote sensing instruments (HSRL-2) and in-situ observations of aerosol optical properties calculated from size distributions measured aboard the DoE G-1 aircraft. Chapter 5 also includes a discussion on the effects of dry, moist, and size-corrections that need to be applied to the in-situ observations in order to infer extinction in the atmosphere. In the final Chapter 6, I present a comprehensive analysis of CHOCHO, HCHO, and NO2 column measurements obtained in multiple field deployments of MAX-DOAS under different NOx (NO + NO2) conditions and VOC precursors. In particular, I assess the magnitude of the ratio of CHOCHO to HCHO (RGF ), which has been proposed as a metric to distinguish biogenic and/or anthropogenic VOC (BVOC/AVOC) influences, and show with box-modeling that the concentration of NO2 and dictates the value of RGF . I proposed a new metric of RGF based on box-modeling and field measurements to distinguish AVOC/BVOC influences and split in BVOCs