Elevated methylmercury production in seasonally inundated sediments: Insights from DOM molecular composition

Abstract

Seasonally inundated areas (SIA) within aquatic systems are characterized by elevated methylmercury (MeHg) production. Nevertheless, the response characteristics of dissolved organic matter (DOM) quality in SIA sediments, including its molecular compositions and structure, and their impacts on the MeHg production are not yet fully understood. This research gap has been addressed through field investigations and microcosm experiments conducted in a metal-polluted plateau wetland. The results revealed that DOM_SIA had lower levels of chromophoric DOM concentrations, protein-like fractions, molecular complexity, and debris size while exhibiting higher humic-like fractions, molecular weight, COO- groups, and bioavailability than DOM in permanently inundated areas (PIA). Compared with DOM_PIA, DOM_SIA was more easily biodegraded, and exhibited a higher adsorption capacity while lower binding affinity for Hg(Ⅱ). Moreover, MeHg synthesis by Desulfomicrobium escambiense was 29.6-fold higher in DOM_SIA than that in DOM_PIA, and DOM_SIA amendment also resulted in a higher MeHg production in the sediment. The PLS-PM model demonstrated that DOM compositions positively showed high contributions to MeHg levels in sediment porewater (0.51), while binding affinity had a negative pattern (-0.83), but adsorption capacity had a lower contribution (0.09). These findings provide an updated explanation for the elevated MeHg level in the SIA of aquatic systems, which are closely related to the adaptive response of DOM molecular composition and structure in the sediment.