ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-3557-2012 Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry Altieri K. E. 1 Hastings M. G. 2 Peters A. J. 3 Sigman D. M. 1 Department of Geosciences, Princeton University, Princeton, NJ, USA Department of Geological Sciences & Environmental Change Initiative, Brown University, Providence, RI, USA Bermuda Institute of Ocean Sciences, St. Georges, Bermuda 12 04 2012 12 7 3557 3571 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/12/3557/2012/acp-12-3557-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/3557/2012/acp-12-3557-2012.pdf

Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W), which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2281 N containing compounds were determined over the mass range <i>m</i>/<i>z</i><sup>+</sup> 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+), CHON compounds that contained sulfur (CHONS+), CHON compounds that contained phosphorus (CHONP+), CHON compounds that contained both sulfur and phosphorus (CHONSP+), and compounds that contained only carbon, hydrogen, and nitrogen (CHN+). Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Despite their prevalence in continental rainwater, no organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March) which have anthropogenic air mass origins and samples collected during the warm season (April to September) with remote marine air mass origins. This, in conjunction with patterns identified in van Krevelen diagrams, suggests that the cold season WSON is a mixture of organic matter with both marine and anthropogenic sources while in the warm season the WSON appears to be dominated by marine sources. These findings indicate that, although the concentrations and percent contribution of WSON to total N is fairly consistent across diverse geographic regions, the chemical composition of WSON varies strongly as a function of source region and atmospheric environment.

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