Molecular composition difference of electron donating moieties between natural organic matter and effluent organic matter probed by chlorine dioxide

Abstract

Lignin- and tannin-like phenolic compounds are shown to be the major compositions of electron donating moieties (EDM) of aquatic natural organic matter (NOM). However, little is known about the compositions of EDMs within effluent organic matter (EfOM). In the present study, chlorine dioxide (ClO₂) was used as a selectively oxidative probe to investigate the difference in the molecular composition of EDM between NOM and EfOM due to its high selectivity towards electron-rich compounds. The results showed that there was a large difference in the bulk and molecular properties of ClO₂-reactive moieties between EfOM and NOM. Specifically, ClO₂-reactive moieties of EfOM are distributed in a narrower molecular weight range (i.e., 0.9 kDa to 3.0 kDa) compared to NOM (i.e., 1.0 kDa to 20 kDa). The molecular-level analysis demonstrated that highly aromatic, reduced formulas (O/C = 0.33 ± 0.16; H/C = 1.10 ± 0.34) referring the lignin- and tannin-like compounds within both NOM and EfOM were susceptible to oxidation by ClO₂, while more saturated formulas including the peptide-like formulas (H/C = 1.59 ± 0.36) within EfOM were reactive towards ClO₂. Furthermore, the nitrogen (N)-containing formulas in EfOM are suggested to be the major EDMs compared to the CHO-only formulas dominating the EDM in NOM. This study has important implications for understanding of the origin and chemical nature of EDM in DOM from various sources and provides molecular-level evidence for the selectivity of ClO₂ as an oxidant towards DOM.