Relationship between Molecular Components and Reducing Capacities of Humic Substances

Humic substances (HSs) are collections of diverse organic compounds with broad redox capacities, which directly or indirectly affect the biogeochemical behaviors and fates of almost all the pollutants in the environment. The present study investigates the relationships between the molecular characteristics of HSs and their reducing capacities or electron-donating capacities (EDCs) by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), total phenolic assay, and mediated electrochemical oxidation analysis. For decreasing the molecular heterogeneity of bulk HSs, HSs were first separated into three fractions according to their polarities. The results demonstrated that compounds in HS fractions with moderate polarity possessed a high content of total phenols and consistently had high EDCs. A strong linear correlation (R2 = 0.97) existed between EDCs and the total phenolic content, which confirmed that phenols contributed to the EDCs of HSs. Further analysis of molecular components confirmed that polyphenol-like compounds with medium oxygen content were the major moieties acting as electron donors in HSs. This study provides a linkage between the molecular components of HSs and their EDCs, which will help us to understand the molecular-dependent reducing properties of HSs or other dissolved organic matters under oxic conditions.