ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-10-11359-2010 Ship-based detection of glyoxal over the remote tropical Pacific Ocean Sinreich R. 1 Coburn S. 1 Dix B. 1 Volkamer R. 1 2 Department of Chemistry and Biochemistry, University of Colorado at Boulder, Colorado, USA Cooperative Institute for Research in the Environmental Studies, Boulder, Colorado, USA 01 12 2010 10 23 11359 11371 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/10/11359/2010/acp-10-11359-2010.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/11359/2010/acp-10-11359-2010.pdf

We present the first detection of glyoxal (CHOCHO) over the remote tropical Pacific Ocean in the Marine Boundary Layer (MBL). The measurements were conducted by means of the University of Colorado Ship Multi-Axis Differential Optical Absorption Spectroscopy (CU SMAX-DOAS) instrument aboard the research vessel Ronald H. Brown. The research vessel was on a cruise in the framework of the VAMOS Ocean-Cloud-Atmosphere-Land Study – Regional Experiment (VOCALS-REx) and the Tropical Atmosphere Ocean (TAO) projects lasting from October 2008 through January 2009 (74 days at sea). The CU SMAX-DOAS instrument features a motion compensation system to characterize the pitch and roll of the ship and to compensate for ship movements in real time. We found elevated mixing ratios of up to 140 ppt CHOCHO located inside the MBL up to 3000 km from the continental coast over biologically active upwelling regions of the tropical Eastern Pacific Ocean. This is surprising since CHOCHO is very short lived (atmospheric life time ~2 h) and highly water soluble (Henry's Law constant <i>H</i> = 4.2 × 10<sup>5</sup> M/atm). This CHOCHO cannot be explained by transport of it or its precursors from continental sources. Rather, the open ocean must be a source for CHOCHO to the atmosphere. Dissolved Organic Matter (DOM) photochemistry in surface waters is a source for Volatile Organic Compounds (VOCs) to the atmosphere, e.g. acetaldehyde. The extension of this mechanism to very soluble gases, like CHOCHO, is not straightforward since the air-sea flux is directed from the atmosphere into the ocean. For CHOCHO, the dissolved concentrations would need to be extremely high in order to explain our gas-phase observations by this mechanism (40–70 μM CHOCHO, compared to ~0.01 μM acetaldehyde and 60–70 μM DOM). Further, while there is as yet no direct measurement of VOCs in our study area, measurements of the CHOCHO precursors isoprene, and/or acetylene over phytoplankton bloom areas in other parts of the oceans are too low (by a factor of 10–100) to explain the observed CHOCHO amounts. We conclude that our CHOCHO data cannot be explained by currently understood processes. Yet, it supports first global source estimates of 20 Tg/year CHOCHO from the oceans, which likely is a significant source of secondary organic aerosol (SOA). This chemistry is currently not considered by atmospheric models.

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