Document Type

Dissertation

Date of Degree

Spring 2015

Degree Name

PhD (Doctor of Philosophy)

Degree In

Chemistry

First Advisor

Vicki H. Grassian

Abstract

Aerosols are important atmospheric constituents that impact the Earth's radiative balance and climate. The detailed knowledge of the aerosol optical properties is required for a comprehensive analysis of the impacts of aerosols on climate. Mie theory is often used in satellite and ground-based retrieval algorithms to account for atmospheric mineral dust. However, the approximations used in Mie theory are often not appropriate for mineral dust and can lead to errors in the optical properties modeling. Analytic models based on Rayleigh theory that account for particle shapes can offer significant advantages when used to model infrared (IR) extinction of mineral dust. Here, the IR optical properties of some components of mineral dust, authentic dust samples and minerals processed with organic acids were investigated. Detailed characterization of the particles through online and offline methods of analysis that include IR extinction spectroscopy, micro-Raman spectroscopy and scanning electron microscopy was performed. Analysis of the IR extinction spectra and spectral simulations showed that the positions of the peaks and the shapes of the bands of the IR characteristic features are not well simulated by Mie theory in any of the samples studied. The resonance peaks were consistently shifted relative to the experimental spectrum in the Mie simulation. Rayleigh model solutions derived for different particle shapes better predicted the peak positions and band shapes of experimental spectra. To fill the gaps in the refractive index data for atmospherically relevant organic compounds in the IR region optical properties of atmospherically relevant carboxylic acids and humic-like substances using the IR extinction spectra and size distributions measured in the laboratory were determined.

In addition to properties of mineral dust this dissertation focuses on properties of sea spray aerosol. Chemical and elemental composition of individual sea spray aerosol particles were studies using micro-Raman spectroscopy, mass-spectrometry and X-ray spectroscopy to provide insights into the biochemical processes that give rise to classes of organic molecules that make up these aerosol particles. The results suggested that degradation of biota (bacteria and diatoms) present in sea water led to lipopolysaccharides and extracellular polymeric substances that further degraded down to carbohydrates and fatty acids. Solubility of the resulting organic species seemed to play a role in their transfer to the aerosol phase. Furthermore, water uptake and hygroscopic growth of multi-component particles were studied. Understanding the interactions of water with atmospheric aerosols is crucial for determining their size, physical state, reactivity, and therefore for aerosol interactions with electromagnetic radiation and clouds. It was determined that particles composed of ammonium sulfate with succinic acid and of mixture of chlorides typical for marine environment show size dependent hygroscopic behavior. Microscopic analysis of the distribution of components within the aerosol particles showed that the observed size dependence is due to the differences in the mixing state. The composition and water uptake properties of sea spray aerosol particles were also measured during a phytoplankton bloom. The results showed that water uptake properties were directly related to the chemical composition of the particles and hygroscopicity decreased with increase in the fraction of water insoluble organic matter emitted during phytoplankton bloom. Finally, multiple methods of particle size, phase and shape analysis were compared and the results showed that the techniques that operate under ambient conditions provide the most relevant and robust measurement of particle size. Additionally, several storage methods for substrate deposited aerosol particles were evaluated and it was determined that storing samples at low relative humidity led to irreversible changes due to sample dehydration while sample freezing and thawing leads to irreversible changes due to phase changes and water condensation. Therefore it is suggested that samples used for single-particles analysis should be stored at ambient laboratory conditions, or near conditions which they were collected, in order to preserve the sample phase and hydration state.

The results presented in this dissertation provide insight into physicochemical properties of atmospheric aerosols and help us better understand the role of aerosol particles in the Earth's atmosphere.

Public Abstract

Aerosol is a mixture of liquid or solid particles in the air. Aerosols are important for the Earth’s atmosphere. They can interact with sunlight, water vapor and react with gases in the atmosphere and therefore have an effect on climate. In this dissertation, the composition and properties of mineral dust (wind-blown soil particles) and sea spray aerosol (particles produced from the ocean surface) were studied. Different theories predict how aerosol particles interact with sunlight and heat emitted from the Earth's surface. Here we investigated how two of these theories, Mie and Rayleigh theory, predict properties of fresh mineral particles, mineral particles reacted with acids and natural dust particles (e.g. Saharan sand). Results showed that Rayleigh theory works better for all the samples studied here. Particles collected from the seawater were analyzed and their chemical composition was studied. The results suggested that the organic compounds observed in these particles are formed upon the death and degradation of the organisms present in the ocean and a pathway of the degradation is suggested based on the analysis. Additionally, interactions of marine aerosol particles with water were studied. It was shown that interactions with water can depend on the size of the particles and their chemical composition. The results presented in this dissertation help us better understand aerosols and their role in the Earth’s atmosphere.

Keywords

publicabstract, Aerosol, Mineral dust, Radiative forcing, Sea spray, Water uptake

Pages

xxix, 321

Bibliography

298-321

Copyright

Copyright 2015 Olga Laskina

Included in

Chemistry Commons

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