Sea spray aerosol (SSA) particles represent one of the most abundant surfaces available for heterogeneous reactions to occur upon and thus profoundly alter the composition of the troposphere. In an effort to better understand tropospheric heterogeneous reaction processes, fundamental laboratory studies must be able to accurately reproduce the chemical complexity of SSA. Here we describe a new approach that uses microbial processes to control the composition of seawater and SSA particle composition. By inducing a phytoplankton bloom, we are able to create dynamic ecosystem interactions between marine microorganisms, which serve to alter the organic mixtures present in seawater. Using this controlled approach, changes in seawater composition become reflected in the chemical composition of SSA particles 4 to 10 d after the peak in chlorophyll-a. This approach for producing and varying the chemical complexity of a dominant tropospheric aerosol provides the foundation for further investigations of the physical and chemical properties of realistic SSA particles under controlled conditions.

Abstract. Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be underpinned by a physically and chemically accurate representation of the bubble-mediated production of nascent SSA particles. Bubble bursting is sensitive to the physicochemical properties of seawater. For a sample of seawater, any important differences in the SSA production mechanism are projected into the composition of the aerosol particles produced. Using direct chemical measurements of SSA at the single-particle level, this study presents an intercomparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging-waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than those produced by sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic-enriched particles and a different size-resolved elemental composition, especially in the 0.8-2 µm dry diameter range. Interestingly, chemical differences between the methods only emerged when the particles were chemically analyzed at the single-particle level as a function of size; averaging the elemental composition of all particles across all sizes masked the differences between the SSA samples. When dried, SSA generated by the sintered glass filters had the highest fraction of particles with spherical morphology compared to the more cubic structure expected for pure NaCl particles produced when the particle contains relatively little organic carbon. In addition to an intercomparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method on SSA composition was undertaken. In organic-enriched seawater, the continuous operation of the plunging waterfall resulted in the accumulation of surface foam and an over-expression of organic matter in SSA particles compared to those produced by a pulsed plunging waterfall. Throughout this set of experiments, comparative differences in the SSA number size distribution were coincident with differences in aerosol particle composition, indicating that the production mechanism of SSA exerts important controls on both the physical and chemical properties of the resulting aerosol with respect to both the internal and external mixing state of particles. This study provides insight into the inextricable physicochemical differences between each of the bubble-mediated SSA generation mechanisms tested and the aerosol particles that they produce, andPublished by Copernicus Publications on behalf of the European Geosciences Union.

Understanding the interactions of water with atmospheric aerosols is crucial for determining the size, physical state, reactivity, and climate impacts of this important component of the Earth’s atmosphere. Here we show that water uptake and hygroscopic growth of multicomponent, atmospherically relevant particles can be size dependent when comparing 100 nm versus ca. 6 μm sized particles. It was determined that particles composed of ammonium sulfate with succinic acid and of a mixture of chlorides typical of the marine environment show size-dependent hygroscopic behavior. Microscopic analysis of the distribution of components within the aerosol particles show that the size dependence is due to differences in the mixing state, that is, whether particles are homogeneously mixed or phase separated, for different sized particles. This morphology-dependent hygroscopicity has consequences for heterogeneous atmospheric chemistry as well as aerosol interactions with electromagnetic radiation and clouds.

Abstract. Controlled laboratory studies of the physical and chemical properties of sea spray aerosol (SSA) must be underpinned by a physically and chemically accurate representation of the bubble mediated production of nascent SSA particles. Since bubble bursting is sensitive to the physicochemical properties of seawater, any important differences in the SSA production mechanism are projected into SSA composition. Using direct chemical measurements of SSA at the single-particle level, this study presents an inter-comparison of three laboratory-based, bubble-mediated SSA production schemes: gas forced through submerged sintered glass filters ("frits"), a pulsed plunging waterfall apparatus, and breaking waves in a wave channel filled with natural seawater. The size-resolved chemical composition of SSA particles produced by breaking waves is more similar to particles produced by the plunging waterfall than sintered glass filters. Aerosol generated by disintegrating foam produced by sintered glass filters contained a larger fraction of organic enriched particles and a different size-resolved elemental composition, especially in the 0.8–2 μm size range. These particles, when dried, had more spherical morphologies compared to the more cubic structure expected for pure NaCl particles, which can be attributed to the presence of additional organic carbon. In addition to an inter-comparison of three SSA production methods, the role of the episodic or "pulsed" nature of the waterfall method utilized in this study on SSA composition was undertaken. In organic-enriched seawater, the continuous operation of the plunging waterfall mechanism resulted in the accumulation of surface foam and an over-expression of organic matter in SSA particles compared to pulsed plunging waterfall. Throughout this set of experiments, comparative differences in the SSA number size distribution were coincident with differences in aerosol composition, indicating that the production mechanism of SSA exerts important controls on both the physical and chemical properties of the resulting aerosol. This study provides insight into the physicochemical differences between each of these bubble-mediated SSA generation mechanisms and serves as a guideline for future laboratory studies of SSA particles.

Atmospheric aerosols are often collected on substrates and analyzed weeks or months after the initial collection. We investigated how the selection of substrate and microscopy method influence the measured size, phase, and morphology of sea spray aerosol (SSA) particles and how sample storage conditions affect individual particles using three common microscopy techniques: optical microscopy, atomic force microscopy, and scanning electron microscopy. Micro-Raman spectroscopy was used to determine changes in the water content of stored particles. The results show that microscopy techniques operating under ambient conditions provide the most relevant and robust measurement of particle size. Samples stored in a desiccator and at ambient conditions leads to similar sizes and morphologies, while storage that involves freezing and thawing leads to irreversible changes due to phase changes and water condensation. Typically, SSA particles are deposited wet and, if possible, samples used for single-particle analysis should be stored at or near conditions at which they were collected in order to avoid dehydration. However, if samples need to be dry, as is often the case, then this study found that storing SSA particles at ambient laboratory conditions (17-23% RH and 19-21 °C) was effective at preserving them and reducing changes that would alter samples and subsequent data interpretation.

_______________________________ Charles O. Stanier _______________________________ Alexei V. Tivanski asked. Specifically, I would like to thank Olga Laskina, as without her, I would never have accomplished much. Thanks to all of my professors in the Chemical & Biochemical Engineering Department at the University of Iowa for passing on some their knowledge and their commitment to educational excellence. Lastly, I would like to thank my advisor, Dr. Vicki Grassian, for sticking with me and supporting me through thick and thin.iv ABSTRACT Currently, there exists a great deal of uncertainty regarding atmospheric aerosols and the role that they play within the Earth's atmosphere. It is known that atmospheric aerosols can play a role in the Earth's climate by scattering and absorbing solar radiation or acting as a cloud condensation nuclei. The purpose of this work is to obtain an improved understanding of the chemistry of atmospheric aerosols to better determine their impacts the environment, air quality, and climate.This work revolves around one specific type of atmospheric aerosol, i.e. sea spray aerosol.Sea spray aerosol is generated via breaking waves, through wind-driven mechanisms. Ocean water covers roughly 71% of the Earth's surface, and from this over 1300 Tg of sea spray aerosols is emitted into the atmosphere every year. However, until recently, the study of sea spray was very challenging and often inconclusive due to the inability to filter background particles out. In this work, the understanding of sea spray aerosol is progressed by taking a two-pronged approach.First, this work focuses on the study of model systems of simple ocean surfactants and NaCl and the change in chemistry that occurs when the two are in the presence of each other. Second, sea spray samples generated during a biological bloom are isolated and analyzed. Using this two pronged approach, it is shown that model systems can provide supporting evidence for hypotheses created from trends discovered in more complex samples. Finally, common aerosol generation, storage, and analysis techniques are studied in order to improve our understanding of their effects on aerosol particles. v PUBLIC ABSTRACT For many decades, global warming has been a worldwide concern due to its potential harmful effects on society. In addition to the more commonly known cause of this global phenomenon, greenhouse gases, another important component of the Earth's atmosphere is atmospheric aerosols. Atmospheric aerosols are small, solid and/or liquid particles suspended in the air that vary greatly in size and chemical composition. Much of these variations are a result of the wide variety of natural and man-made sources that emit aerosols into the atmosphere. Like greenhouse gases, these particles can significantly influence the Earth's climate. However, in contrast to greenhouse gases, it is not well understood as how and to what extent, do aerosols impact the climate.In this work, we learn more about one of the most abundant types of atmospheric aerosol, namely se...