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JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 111, D03302, doi:10.1029/2005JD006265, 2006

Photochemical oxidation and changes in molecular composition of organic aerosol in the regional context

Allen L. Robinson

Departments of Mechanical Engineering and Engineering and Public Policy, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


Neil M. Donahue

Departments of Chemical Engineering and Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania, USA


Wolfgang F. Rogge

Department of Civil and Environmental Engineering, Florida International University, Miami, Florida, USA


Abstract

This paper presents evidence that condensed-phase organic compounds are significantly oxidized in regional air masses and in locations affected by regional transport, especially during the summer. The core of the paper examines a large data set of ambient organic aerosol concentrations for removal of reactive compounds relative to less-reactive compounds. The approach allows visualization of both photochemistry and mixing of emissions from multiple sources in order to differentiate between the two phenomena. The focus is on hopanes and alkenoic acids, important markers for motor vehicle and cooking emissions. Ambient data from Pittsburgh, PA and the Southeastern United States contain evidence for significant photochemical oxidation of these compounds in the summertime. There is a strong seasonal pattern in the ratio of different hopanes to elemental carbon consistent with oxidation. In addition, measurements at rural sites indicate that hopanes are severely depleted in the regional air mass during the summer. Alkenoic acids also appear to be photochemically oxidized during the summertime; however, the oxidation rate appears to be much slower than that inferred from laboratory experiments. The significance of photochemistry is supported by rudimentary calculations which indicate substantial oxidation by OH radicals and ozone on a time scale of a few days or so, comparable to time scales for regional transport. Oxidation is non-linear; therefore it represents a very substantial complication to linear source apportionment techniques such as the Chemical Mass Balance model.

Received 23 May 2005; accepted 8 November 2005; published 7 February 2006.

Keywords: organic aerosol; regional transport; molecular markers.

Index Terms: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801, 4906); 0317 Atmospheric Composition and Structure: Chemical kinetic and photochemical properties; 0345 Atmospheric Composition and Structure: Pollution: urban and regional (0305, 0478, 4251).

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Citation: Robinson, A. L., N. M. Donahue, and W. F. Rogge (2006), Photochemical oxidation and changes in molecular composition of organic aerosol in the regional context, J. Geophys. Res., 111, D03302, doi:10.1029/2005JD006265.