Issue 17, 2013

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

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

Supplementary files

Article information

Article type
Paper
Submitted
03 Nov 2012
Accepted
18 Feb 2013
First published
19 Feb 2013
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2013,15, 6206-6214

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. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements