Data evaluation strategy for identification of key molecular formulas in dissolved organic matter as proxies for biogeochemical reactivity based on abundance differences from ultrahigh resolution mass spectrometry

The molecular composition of dissolved organic matter (DOM) is of relevance for global carbon cycling and important for drinking water processing also. The detection of variation of DOM composition as function of time and space from a methodological viewpoint is essential to observe DOM processing and was addressed so far. High resolution concerning DOM quality was achieved with Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS). However almost none of the existing FTICR-MS data sets were evaluated addressing the fate of single mass features / molecular formulas (MFs) abundance during experiments. In contrast to former studies we analyze the function of MF abundance of time and space for such MFs which are present in all samples and which were formerly claimed as recalcitrant in not all but a great number of studies. For the first time the reactivity of MFs was directly compared by their abundance differences using a simple equation, the relative intensity difference (delta RI). Search strategies to find out the maximum delta RI values are introduced. The corresponding MFs will be regarded as key MFs (KEY-MFs). In order to test this new approach data from a recent photo degradation experiment were combined with monitoring surveys conducted in two drinking water reservoirs. The delta RI values varied over one order of magnitude (more than five-fold). MFs like C9H12O6 and C10H14O6 revealed high biogeochemical reactivity as photo products. Some of the KEY-MFs were identical with MFs identified as disinfection byproducts precursors in recent studies. Other KEY-MFs were oxygen-rich and relatively unsaturated (poly-phenol-like) and hence relevant to flocculation procedures.

Automated summary

The molecular composition of dissolved organic matter (DOM) was analyzed using Fourier-transform ion cyclotron resonance mass spectrometry (FTICR-MS) to identify key MFs. The reactivity of these key MFs was compared using a simple equation, the delta RI, and their importance for photo degradation and drinking water processing was determined.