Electron-Donating Phenolic and Electron-Accepting Quinone Moieties in Peat Dissolved Organic Matter: Quantities and Redox Transformations in the Context of Peat Biogeochemistry

Electron-donating phenolic and electron-accepting quinone moieties in peat dissolved organic matter (DOM) are considered to play key roles in processes defining carbon cycling in northern peatlands. This work advances a flow-injection analysis system coupled to chronoamperometric detection to allow for the simultaneous and highly sensitive determination of these moieties in dilute DOM samples. Analysis of anoxic pore water and oxic pool water samples collected across an ombrotrophic bog in Sweden demonstrated the presence of both phenolic and quinone moieties in peat DOM. The pore water DOM had higher quantities of phenolic but not quinone moieties compared with commonly used model aquatic and terrestrial DOM isolates. Significantly lower phenol content in DOM from oxic pools than DOM from anoxic pore waters indicated oxidative DOM processing in the pools. Consistently, treatment of peat DOM with laccase, a phenol-oxidase, under oxic conditions resulted in an irreversible removal of phenols and reversible oxidation of hydroquinones to quinones. Electron transfer to peat DOM was fully reversible over an electrochemical reduction and subsequent O-2-reoxidation cycle, supporting that quinones in peat DOM serve as regenerable microbial electron acceptors in peatlands. The results advance our understanding of redox processes involving phenolic and quinone DOM moieties and their roles in northern peatland carbon cycling.