Jump to main content
Jump to site search

Issue 17, 2013
Previous Article Next Article

Raman microspectroscopy and vibrational sum frequency generation spectroscopy as probes of the bulk and surface compositions of size-resolved sea spray aerosol particles

Author affiliations

Abstract

Sea spray aerosol (SSA) represents one of the largest aerosol components in our atmosphere. SSA plays a major role in influencing climate; however the overall impacts remain poorly understood due to the overall chemical complexity. SSA is comprised of a mixture of inorganic and organic components in varying proportions that change as a function of particle size and seawater composition. In this study, nascent SSA particles were produced using breaking waves, resulting in compositions and sizes representative of the open ocean. The composition of individual SSA particles ranging in size from ca. 0.15 to 10 μm is measured using Raman microspectroscopy, while the interfacial composition of collections of size-resolved particles is probed by sum frequency generation (SFG). Raman spectra of single particles have bands in the 980 to 1030 cm−1 region associated with the symmetric stretch of the sulfate anion, the 2800 to 3000 cm−1 region associated with carbon–hydrogen stretches, and from 3200–3700 cm−1 associated with the oxygen–hydrogen stretches of water. The relative intensities of these features showed a strong dependence on particle size. In particular, submicrometer particles exhibited a larger amount of organic matter compared to supermicrometer particles. However, for external surfaces of homogeneous SSA particles (i.e. particles without a solid inclusion), and also the interfaces of mixed-phase particles, there was a strong SFG response in the aliphatic C–H stretching region for both sub- and supermicrometer particles. This finding suggests that organic material present in supermicrometer particles primarily resides at the interface. The presence of methylene contributions in the SFG spectra indicated disordered alkyl chains, in contrast to what one might expect for a surfactant layer on a sea salt particle. Changes in peak frequencies and relative intensities in the C–H stretching region are seen for some particles after the addition of bacteria, phytoplankton, and growth medium to the seawater. This study provides new insights into the bulk and surface composition of SSA particles and represents a step forward in our understanding of this globally abundant aerosol. It also provides insights into the development of model systems for SSA that may more accurately represent the organic layer at the surface.

Graphical abstract: Raman microspectroscopy and vibrational sum frequency generation spectroscopy as probes of the bulk and surface compositions of size-resolved sea spray aerosol particles

Back to tab navigation

Supplementary files

Publication details

The article was received on 03 Nov 2012, accepted on 18 Feb 2013 and first published on 19 Feb 2013


Article type: Paper
DOI: 10.1039/C3CP43899F
Citation: Phys. Chem. Chem. Phys., 2013,15, 6206-6214
  • Open access: Creative Commons BY license
  •   Request permissions

    Raman microspectroscopy and vibrational sum frequency generation spectroscopy as probes of the bulk and surface compositions of size-resolved sea spray aerosol particles

    A. P. Ault, D. Zhao, C. J. Ebben, M. J. Tauber, F. M. Geiger, K. A. Prather and V. H. Grassian, Phys. Chem. Chem. Phys., 2013, 15, 6206
    DOI: 10.1039/C3CP43899F

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements