Two Dimensional Correlation Analysis of Fourier Transform Ion Cyclotron Resonance Mass Spectra of Dissolved Organic Matter: A New Graphical Analysis of Trends

Abstract

Two-dimensional (2D) correlation analysis was applied to 20 Fourier transform ion cyclotron resonance mass spectra (FTICR-MS) of ultrafiltered dissolved organic matter samples from a salinity transect of the lower Chesapeake Bay. We were able to investigate the chemical changes in the dissolved organic matter pool at the molecular level and classify the individual peaks based on their biogeochemical reactivity. The power of this technique is its ability to be used on either the presence/absence of the individual peaks or their normalized magnitudes. The presence or absence of the peaks are utilized to identify the reactivity and correlation between peaks that plot in different regions of the van Krevelen diagram, whereas the normalized magnitudes are used to correlate the changes among individual peaks. One of the promising advantages of 2D correlation of FTICR-MS data is the ability to associate the variations of the individual peaks with the changes in the functional groups that are measured by other spectroscopic techniques. This approach takes us one step further from identifying molecular formulas to proposing chemical structures.