Molecular-scale investigation of soil fulvic acid and water-extractable organic matter by high-resolution mass spectrometry and 1H NMR spectroscopy

Environmental contextNotwithstanding the environmental and geochemical significance of soil dissolved organic matter (DOM), its molecular components are still not well characterised. This study investigates chemical similarities and differences between two widely used forms of soil DOM: water-extractable organic matter and fulvic acids. The findings will guide appropriate extraction and purification protocols in future studies related to soil DOM. AbstractDissolved organic matter (DOM) is the most active fraction of soil organic matter (SOM), which has both environmental and geochemical importance. However, the extraction of DOM from soils is still ambiguous. Instead, operational concepts, such as fulvic acid (FA) and water-extractable organic matter (WEOM), are widely used in practice. In this study, the molecular components of FA and WEOM extracted from two standard soils were investigated by using electrospray ionisation coupled with Fourier-transform ion cyclotron resonance mass spectrometry and proton nuclear magnetic resonance (1H NMR) spectroscopy to clarify the molecular similarities and differences between them. The results revealed that WEOM and FA shared many of the same molecules, which accounted for 64% and 82% of the total numbers of molecules for WEOM and FA respectively. However, WEOM displayed higher chemical and molecular diversities than FA. Detailed analysis revealed that the extraction and desalination procedure of FA led to the loss of lignin, protein and carbohydrate compounds, but induced preferential release of some tannin-like molecules from the aggregate- or organic mineral-associated SOM. Based on the results of the present study, water extraction combined with desalination through a functionalised styrene divinylbenzene polymer-based solid phase extraction is more reliable to retain the molecular diversity of soil DOM.