Articles | Volume 13, issue 9
Atmos. Chem. Phys., 13, 4829–4838, 2013
Atmos. Chem. Phys., 13, 4829–4838, 2013

Research article 14 May 2013

Research article | 14 May 2013

Insights into dissolved organic matter complexity in rainwater from continental and coastal storms by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry

R. N. Mead1, K. M. Mullaugh1, G. Brooks Avery1, R. J. Kieber1, J. D. Willey1, and D. C. Podgorski2 R. N. Mead et al.
  • 1Department of Chemistry and Biochemistry University of North Carolina, Wilmington, NC 28403-5932, USA
  • 2National High Magnetic Field Laboratory 1800 East Paul Dirac Dr., Tallahassee, FL 32310-4005, USA

Abstract. A series of seven rainwater samples were collected in Wilmington, North Carolina USA originating from both continental and coastal storms and analyzed by ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). This data set is unique in that it represents a detailed comparison of the molecular level composition of DOM in rainwater collected from distinctly different air mass back trajectories by FT-ICR MS. Approximately 25% of the roughly 2000 assigned CHO molecular formulas are unique to a single storm classification indicating the importance of air mass back trajectory on the composition of rainwater dissolved organic matter (DOM). Analysis of the unique molecular formula assignments highlighted distinct groupings of various bio- and geo-molecule classes with coastal storms containing unique formulas representative of lignin and cellulose-like formulas while continental storms had lipid-like formulas. A series of 18 distinct methylene oligomers were identified in coastal storms and 13 unique methylene oligomers in continental storms, suggesting oligomer formation is ubiquitous in rainwater albeit different for each storm classification. Oligomers of small acids and C3H4O2 were detected in both storm types indicating their processing may be similar in both back trajectories. Condensed aromatic hydrocarbons were detected in continental storms with phenol moieties that are not as oxidized as similar compounds detected in aquatic DOM.

Final-revised paper