Molecular insights into the bonding mechanisms between selenium and dissolved organic matter.

Natural organic matter (NOM) plays a critical role in the mobilization and bioavailability of metals and metalloids in the aquatic environment. Selenium (Se), an environmental contaminant of aquatic systems, has drawn increasing attention over the years. While Se is a vital micronutrient to human beings, animals and plants, excess Se intake may pose serious long-term risks. However, the interaction between Se and dissolved organic matter (DOM) remains relatively unexplored, especially the reaction mechanisms and interactions of specific NOM components of certain molecular weight and the corresponding functional group change. Herein, we report an investigation on the interactions between Se and DOM by focusing on the mass distribution profile change of operationally defined molecular weight fractions of humic acid (HA) and fulvic acid (FA). The results showed that across all molecular weights studied, HA fractions were more prone to enhanced aggregation upon introduction of Se into the system. For FA, the presence of Se species results in aggregation, dissociation, and redox reactions with the first two being the major mechanisms. Total organic carbon analysis (TOC), UV-vis spectroscopy (UV-vis), and Orbitrap MS data showed that [10, 30] kDa MW fraction had the largest aromatic decrease (CRAM-like, lignin-like and tannin-like) upon addition of SeO