Influence of heteroatom pre-selection on the molecular formula assignment of soil organic matter components determined by ultrahigh resolution mass spectrometry.

Soil organic matter (SOM) is involved in many important ecosystem processes. Ultrahigh resolution mass spectrometry has become a powerful technique in the chemical characterization of SOM, allowing assignment of elemental formulae for thousands of peaks resolved in a typical mass spectrum. We investigated how the addition of N, S, and P heteroatoms in the formula calculation stage of the mass spectra processing workflow affected the formula assignments of mass spectra peaks. Dissolved organic matter extracted from plant biomass and soil as well as the soil humic acid fraction was studied. We show that the addition of S and P into the molecular formula calculation increased peak assignments on average by 17.3 % and 10.7 %, respectively, over the assignments based on the CHON elements frequently reported by SOM researchers using ultrahigh resolution mass spectrometry. The organic matter chemical characteristics as represented by van Krevelen diagrams were appreciably affected by differences in the heteroatom pre-selection for the three organic matter samples investigated, especially so for the wheat-derived dissolved organic matter. These results show that inclusion of both S and P heteroatoms into the formula calculation step, which is not routinely done, is important to obtain a more chemically complete interpretation of the ultrahigh resolution mass spectra of SOM.