Interactions of anthropogenic and terrestrial sources drive the varying trends in molecular chemodiversity profiles of DOM in urban storm runoff, compared to land use patterns

Variations in land use drive the heterogeneous nature of dissolved organic matter (DOM) in storm runoff. However, in the context of the currently complicated multifactor interactions of urban land use, contamination occurrence, and environmental management, it is unclear how the molecular chemodiversity of storm runoff DOM responds to land use patterns or potential anthropogenic sources. Using Fourier-transform ion cyclotron resonance mass spectrometry, this study evaluated the molecular chemodiversity profiles of DOM in urban storm runoff from different land use and underlying surface pavement combinations. The chemodiversity of suburban forest runoff-associated DOM was characterized by high lignin and tannin abundance, predominance of CHO molecules, less heteroatoms, high molecular mass, and highly unsaturated and aromatic compounds. Urban storm runoff-associated DOM was predominantly characterized by abundant lipids, proteins, and carbohydrates, low-mass molecules, abundant S- and P-bearing heteroatoms, and high saturation. The low conformity of unique molecular features co-occurring across urban land-uses suggests a relatively incohesive pool in the urban storm runoff-associated DOM, i.e., high chemodiversity. The reconstructed source-derived patterns significantly drive the directional trends in DOM of urban storm runoff, oppositely shifting toward high saturation vs. high unsaturation and aromatization features. This demonstrates that unveiling the interactions of anthropogenic and terrestrial sources in order to understand the underlying mechanism is critical for our ability to track and predict the current and future turnover in DOM chemodiversity in storm runoff in the context of the global trend of upgrading urban environment management, following recognition of their probable links with urban land-uses. Underlying surface pavement can hardly superimpose a directional effect to alter the discrepancies in the dominant molecules of each urban land use further. These findings reveal the importance of understanding DOM characteristics at a molecular level and potentially enable targeted control of ecological risks in receiving ecosystems induced by urban storm runoff.