skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Collapse Mechanisms of Nascent and Aged Sea Spray Aerosol Proxy Films
Sea spray aerosol (SSA) is highly enriched in marine-derived organic compounds during seasons of high biological productivity, and saturated fatty acids comprise one of the most abundant classes of molecules. Fatty acids and other organic compounds form a film on SSA surfaces, and SSA particle surface-area-to-volume ratios are altered during aging in the marine boundary layer (MBL). To understand SSA surface organization and its role during dynamic atmospheric conditions, an SSA proxy fatty acid film and its individual components stearic acid (SA), palmitic acid (PA), and myristic acid (MA) are studied separately using surface pressure–area ( Π − A ) isotherms and Brewster angle microscopy (BAM). The films were spread on an aqueous NaCl subphase at pH 8.2, 5.6, and 2.0 to mimic nascent to aged SSA aqueous core composition in the MBL, respectively. We show that the individual fatty acid behavior differs from that of the SSA proxy film, and at nascent SSA pH the mixture yields a monolayer with intermediate rigidity that folds upon film compression to the collapse state. Acidification causes the SSA proxy film to become more rigid and form 3D nuclei. Our results reveal film morphology alterations, which are related to SSA reflectivity, throughout various stages of SSA aging and provide a better understanding of SSA impacts on climate.  more » « less
Award ID(s):
1801971
PAR ID:
10096481
Author(s) / Creator(s):
;
Date Published:
Journal Name:
Atmosphere
Volume:
9
Issue:
12
ISSN:
2073-4433
Page Range / eLocation ID:
503
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al (, Elem Sci Anth)
    The rapidly warming Arctic has transitioned to thinner sea ice which fractures, producing leads. Few studies have investigated Arctic sea spray aerosol (SSA) produced from open ocean, leads, and melt ponds, which vary in salinity and organic and microbial community composition. A marine aerosol reference tank was deployed aboard an icebreaker to the Arctic Ocean during August–September 2018 to study SSA generated from locally collected surface waters. Aerosol generation experiments were carried out using water collected from the marginal ice zone, a human-made hole in sea ice near the North Pole, and both lead and melt pond water during an ice floe drift period. Salinity, chlorophyll a, organic carbon, nitrogen, and microbial community composition were measured. Eukaryotic plankton and bacterial abundance were elevated in experimental water from the marginal ice zone, but the relative contributions from major eukaryotic taxonomic groups varied little across the experiments. The chemical composition of individual SSA particles was analyzed using Raman microspectroscopy and computer-controlled scanning electron microscopy with energy-dispersive X-ray spectroscopy. Individual sea salt aerosol, primary organic aerosol, and mineral dust particles were observed. Sea salt aerosol constituted 44–95% of individual submicrometer and 68–100% of supermicrometer particles, by number, generated during each experiment. Carbon was detected in 85%, by number, of the individual sea salt particles, with visible organic coatings. Carbohydrates were detected in 72% of particles, by number, with smaller contributions from long-chain fatty acids (13%) and siliceous material (15%). SSA generated from melt pond water contained only long-chain fatty acids and siliceous material. Quantification of the ice-nucleating activity showed that locally produced SSA may define the High Arctic background ice-nucleating particle population, but cannot account for the peak atmospheric concentrations observed. As the Arctic warms, the increasing SSA emissions have a complex dependence on changing biological and physical processes. 
    more » « less
  2. ; ; ; ; (, Atmosphere)
    Field measurements have shown that sub-micrometer sea spray aerosol (SSA) is significantly enriched in organic material, of which a large fraction has been attributed to soluble saccharides. Existing mechanistic models of SSA production struggle to replicate the observed enhancement of soluble organic material. Here, we assess the role for divalent cation mediated co-adsorption of charged surfactants and saccharides in the enrichment of soluble organic material in SSA. Using measurements of particle supersaturated hygroscopicity, we calculate organic volume fractions for molecular mimics of SSA generated from a Marine Aerosol Reference Tank. Large enhancements in SSA organic volume fractions (Xorg > 0.2) were observed for 50 nm dry diameter (dp) particles in experiments where cooperative ionic interactions were favorable (e.g., palmitic acid, Mg2+, and glucuronic acid) at seawater total organic carbon concentrations (<1.15 mM C) and ocean pH. Significantly smaller SSA organic volume fractions (Xorg < 1.5 × 10−3) were derived from direct measurements of soluble saccharide concentrations in collected SSA with dry diameters <250 nm, suggesting that organic enrichment is strongly size dependent. The results presented here indicate that divalent cation mediated co-adsorption of soluble organics to insoluble surfactants at the ocean surface may contribute to the enrichment of soluble saccharides in SSA. The extent to which this mechanism explains the observed enhancement of saccharides in nascent SSA depends strongly on the concentration, speciation, and charge of surfactants and saccharides in the sea surface microlayer. 
    more » « less
  3. ; ; (, Environmental Science: Atmospheres)
    The acidity of atmospheric aerosols controls their impacts on heterogeneous and multiphase reactions, cloud formation, and human health. Recently, it has been shown that multiphase buffering can shift aerosol pH substantially compared to bulk solutions. Here, we highlight a unique type of multiphase buffering for aerosols that occurs when organic acids partition from aqueous salt aerosols upon acidification with a strong acid. In this case, rather than lowering the pH of the aerosol, titration with strong acids lowers the organic fraction within the aerosol while maintaining constant pH. We investigate evaporation rates for the model system lactic acid as well as other atmospherically-relevant species such as acetic, butyric, and methacrylic acids. We demonstrate that the timescales for evaporation of organic acids from aerosols are on the order of minutes, comparable to acidification rates in the atmosphere. The organic acid evaporation we observe for lactic acid in salt aerosols is enhanced compared to bulk measurements within what is expected based on differences in surface to volume ratios, indicating surface effects are important. In addition, we show that a salting-out effect drives small organic molecules to the surface, where they quickly evaporate, reducing acidity and causing a “superbuffering” effect. Our results can explain why aerosols in the pH range from 2 to 4 are able to resist further acidification by strong acids in the atmosphere. Overall, this work highlights unique properties of concentrated aerosols and demonstrates how inorganic ions and organic compounds together control multiphase buffering in the atmosphere. 
    more » « less
  4. ; ; ; ; ; ; ; (, Atmospheric Chemistry and Physics)
    Russell, Lynn M (Ed.)
    Abstract. Organic acids represent an important class of compounds in the atmosphere, but there is limited research investigating their chemical production, particularly in the northeast United States. To improve our understanding of organic acid sources, a modeling analysis was performed for air masses reaching the summit of Whiteface Mountain (WFM), New York, where measurements of organic acids in cloud water have been collected. The analysis focuses on a pollution event associated with a heat wave that occurred on 1–2 July 2018 that exhibited unusually high concentrations of formic (HCOOH), acetic (CH3COOH), and oxalic (OxAc) acid in cloud water. The gas-phase production of organic acids for this pollution event was modeled using a combination of the regional transport model Weather Research and Forecasting Model with Chemistry (WRF-Chem), which gives information on transport and environmental factors affecting air parcels reaching WFM, and the Lagrangian chemical box model BOXMOX, which allows analysis of chemistry with different chemical mechanisms. Two chemical mechanisms are used in BOXMOX: (1) the Model for Ozone and Related chemical Tracers (MOZART T1) and (2) the Master Chemical Mechanism (MCM) version 3.3.1. The WRF-Chem results show that air parcels sampled during the pollution event at WFM originated in central Missouri, which has strong biogenic emissions of isoprene. Many air parcels were influenced by emissions of nitrogen oxides (NOx) from the Chicago metropolitan area. The gas-phase oxidation of isoprene and its related oxidation products was the major source of HCOOH and CH3COOH, but both mechanisms substantially underproduced both acids compared to observations. A simple gas–aqueous mechanism was included to investigate the role of aqueous chemistry in organic acid production. Aqueous chemistry did not produce more HCOOH or CH3COOH, suggesting missing chemical sources of both acids. However this aqueous chemistry was able to explain the elevated concentrations of OxAc. Anthropogenic NOx emissions from Chicago had little overall impact on the production of all three organic acids. Further studies are required to better constrain gas and aqueous production of low-molecular-weight organic acids. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; ; et al (, American Association for Aerosol Research)
    Organic compounds in the atmosphere play a pivotal role in atmospheric chemistry, and clouds are significant in the genesis and alteration of these compounds. Di-carboxylic organic anions such as oxalate serve as tracers for aqueous processing. This poster details our findings from summer measurements of three major organic acids (formic acid, acetic acid, oxalic acid), as well as inorganic anions (sulfate, chloride, nitrate) and cations (sodium, potassium, ammonium, calcium, magnesium) in cloud water, aerosol, and cloud droplet residual samples collected at the summit of Whiteface Mountain (WFM) in the Adirondack Mountains, northern New York State. We also evaluate the contribution of these organic acids to water-soluble organic carbon (WSOC) concentrations. Previous studies have explored the oxalate: WSOC ratio with ozone levels, aiming to deduce the influence of biogenic Volatile Organic Compounds (VOCs) on Secondary Organic Aerosol (SOA) formation from nearby forest ecosystems. Our poster presents new observations that significantly broaden this understanding by comparing to diverse global environments and analyzing both cloud water and aerosol phases. Additionally, we introduce oxalate: sulfate ratios from our dataset, proposed by other researchers as a key indicator of aqueous processing due to the enhanced production rates of these ions by liquid water content (sulfate ion) or droplet surface area (oxalate ion). We compare the observed range of oxalate: sulfate ratios with those from field campaigns conducted in other regions. Moreover, for the first time, we examine the relationship between ammonium and organic acids across cloud water, aerosol, and droplet residual samples collected in 2023, and discuss the influence of wildfire smoke on these dynamics. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email