Selective mass labeling for linking the optical properties of chromophoric dissolved organic matter to structure and composition via ultrahigh resolution electrospray ionization mass spectrometry.

The mass spectra acquired by ESI FT-ICR MS of untreated, borohydride-reduced, and borodeuteride-reduced samples of Suwannee River fulvic acid (SRFA) and a C18 extract from the upper Delaware Bay were compared to one another. Treatment of these samples with sodium borodeuteride was shown to produce unique mass labels for species which contain one or two ketone/aldehyde moieties. Approximately 30% of all identified peaks in the two samples were shown to comprise ketone/aldehyde-containing species. The molecular formulas of the majority of these species had O/C and H/C molar ratios typically attributed to lignin-derived compounds and/or carboxylic rich alicyclic molecules (CRAM). However, the significant loss of UV-vis absorption following reduction supports a lignin-based origin for the optical (and photochemical) properties of these samples. The mass-labeling method described and tested herein shows great promise as a means to further characterize the structure and composition of complex natural samples, especially in terms of identifying specific subsets of chemical species that contribute significantly to the optical and photochemical properties of such samples.