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Title: Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity

Abstract

The impact of sea spray aerosol (SSA) on climate depends on the size and chemical composition of individual particles that make-up the total SSA ensemble. While the organic fraction of SSA has been characterized from a bulk perspective, there remains a lack of understanding as to the composition of individual particles within the SSA ensemble. To better understand the molecular components within SSA particles and how SSA composition changes with ocean biology, simultaneous measurements of seawater and SSA were made during a month-long mesocosm experiment performed in an ocean-atmosphere facility. Herein, we deconvolute the composition of freshly emitted SSA devoid of anthropogenic and terrestrial influences by characterizing classes of organic compounds as well as specific molecules within individual SSA particles. Analysis of SSA particles show that the diversity of molecules within the organic fraction varies between two size fractions (submicron and supermicron) with contributions from fatty acids, monosaccharides, polysaccharides and siliceous material. Significant changes in the distribution of these compounds within individual particles are observed to coincide with the rise and fall of phytoplankton and bacterial populations within the seawater. Furthermore, water uptake is impacted as shown by hygroscopicity measurements of model systems composed of representative organic compounds. Thus, themore » how changes in the hygroscopic growth of SSA evolves with composition can be elucidated. Overall, this study provides an important connection between biological processes that control the composition of seawater and changes in single particle composition which will enhances our ability to predict the impact of SSA on climate.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1358472
Report Number(s):
PNNL-SA-117125
Journal ID: ISSN 2451-9294; 48375; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chem; Journal Volume: 2; Journal Issue: 5
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Cochran, Richard E., Laskina, Olga, Trueblood, Jonathan V., Estillore, Armando D., Morris, Holly S., Jayarathne, Thilina, Sultana, Camille M., Lee, Christopher, Lin, Peng, Laskin, Julia, Laskin, Alexander, Dowling, Jacqueline A., Qin, Zhen, Cappa, Christopher D., Bertram, Timothy H., Tivanski, Alexei V., Stone, Elizabeth A., Prather, Kimberly A., and Grassian, Vicki H. Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity. United States: N. p., 2017. Web. doi:10.1016/j.chempr.2017.03.007.
Cochran, Richard E., Laskina, Olga, Trueblood, Jonathan V., Estillore, Armando D., Morris, Holly S., Jayarathne, Thilina, Sultana, Camille M., Lee, Christopher, Lin, Peng, Laskin, Julia, Laskin, Alexander, Dowling, Jacqueline A., Qin, Zhen, Cappa, Christopher D., Bertram, Timothy H., Tivanski, Alexei V., Stone, Elizabeth A., Prather, Kimberly A., & Grassian, Vicki H. Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity. United States. doi:10.1016/j.chempr.2017.03.007.
Cochran, Richard E., Laskina, Olga, Trueblood, Jonathan V., Estillore, Armando D., Morris, Holly S., Jayarathne, Thilina, Sultana, Camille M., Lee, Christopher, Lin, Peng, Laskin, Julia, Laskin, Alexander, Dowling, Jacqueline A., Qin, Zhen, Cappa, Christopher D., Bertram, Timothy H., Tivanski, Alexei V., Stone, Elizabeth A., Prather, Kimberly A., and Grassian, Vicki H. 2017. "Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity". United States. doi:10.1016/j.chempr.2017.03.007.
@article{osti_1358472,
title = {Molecular Diversity of Sea Spray Aerosol Particles: Impact of Ocean Biology on Particle Composition and Hygroscopicity},
author = {Cochran, Richard E. and Laskina, Olga and Trueblood, Jonathan V. and Estillore, Armando D. and Morris, Holly S. and Jayarathne, Thilina and Sultana, Camille M. and Lee, Christopher and Lin, Peng and Laskin, Julia and Laskin, Alexander and Dowling, Jacqueline A. and Qin, Zhen and Cappa, Christopher D. and Bertram, Timothy H. and Tivanski, Alexei V. and Stone, Elizabeth A. and Prather, Kimberly A. and Grassian, Vicki H.},
abstractNote = {The impact of sea spray aerosol (SSA) on climate depends on the size and chemical composition of individual particles that make-up the total SSA ensemble. While the organic fraction of SSA has been characterized from a bulk perspective, there remains a lack of understanding as to the composition of individual particles within the SSA ensemble. To better understand the molecular components within SSA particles and how SSA composition changes with ocean biology, simultaneous measurements of seawater and SSA were made during a month-long mesocosm experiment performed in an ocean-atmosphere facility. Herein, we deconvolute the composition of freshly emitted SSA devoid of anthropogenic and terrestrial influences by characterizing classes of organic compounds as well as specific molecules within individual SSA particles. Analysis of SSA particles show that the diversity of molecules within the organic fraction varies between two size fractions (submicron and supermicron) with contributions from fatty acids, monosaccharides, polysaccharides and siliceous material. Significant changes in the distribution of these compounds within individual particles are observed to coincide with the rise and fall of phytoplankton and bacterial populations within the seawater. Furthermore, water uptake is impacted as shown by hygroscopicity measurements of model systems composed of representative organic compounds. Thus, the how changes in the hygroscopic growth of SSA evolves with composition can be elucidated. Overall, this study provides an important connection between biological processes that control the composition of seawater and changes in single particle composition which will enhances our ability to predict the impact of SSA on climate.},
doi = {10.1016/j.chempr.2017.03.007},
journal = {Chem},
number = 5,
volume = 2,
place = {United States},
year = 2017,
month = 5
}
  • Atmospheric mineral dust particles represent a major component of tropospheric aerosol mass and provide a reactive surface for heterogeneous reactions with trace atmospheric gases (Dentener et al. 1996).Heterogeneous processes alter the chemical balance of the atmosphere and also modify the physicochemical properties of mineral dust particles (Bauer et al. 2004). Organic and inorganic vapors can react with or partition to dust particles and alter their chemical composition (Al-Hosney et al. 2005; Laskin et al. 2005a, 2005b; Liu et al. 2008; Sullivan et al. 2007, 2009a; Sullivan and Prather 2007; Usher et al. 2003). Calcite (CaCO3) is one of the mostmore » reactive components of mineral dust, readily reacting with acidic gases. The fraction of CaCO3 in total dust mineralogy displays large variations between desert regions and other regions of the world as well as between individual mineral particles (Claquin et al. 1999; Jeong 2008; Laskin et al. 2005b; Sullivan et al. 2007). Through reactions with acidic gases CaCO3 can be converted to soluble hygroscopic products including CaCl2 and Ca(NO3)2, and sparingly soluble, non-hygroscopic products including CaSO4 and CaC2O4 (Krueger et al. 2004; Liu et al. 2008; Sullivan et al. 2009a, 2009b).« less
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  • Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less
    Cited by 1
  • Secondary organic aerosol (SOA) is transformed after its initial formation, but this chemical aging of SOA is poorly understood. Experiments were conducted in the Carnegie Mellon environmental chamber to form secondary organic aerosol (SOA) from the photo-oxidation of toluene and other small aromatic volatile organic compounds (VOCs) in the presence of NO x under different oxidizing conditions. The effects of the oxidizing condition on organic aerosol (OA) composition, mass yield, volatility, and hygroscopicity were explored. Higher exposure to the hydroxyl radical resulted in different OA composition, average carbon oxidation state (OS c), and mass yield. The OA oxidation state generallymore » increased during photo-oxidation, and the final OA OS c ranged from –0.29 to 0.16 in the performed experiments. The volatility of OA formed in these different experiments varied by as much as a factor of 30, demonstrating that the OA formed under different oxidizing conditions can have a significantly different saturation concentration. In conclusion, there was no clear correlation between hygroscopicity and oxidation state for this relatively hygroscopic SOA.« less
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