Assessing the Molecular‐Level Controls of Dissolved Organic Matter Cycling in West Siberian Lowland Rivers

Abstract The West Siberian Lowland (WSL) contains some of the largest wetlands and most extensive peatlands on Earth, storing vast amounts of vulnerable carbon across permafrost‐free to continuous permafrost zones. As temperature and precipitation changes continue to alter the Siberian landscape, carbon transfer to the atmosphere and export to the Arctic Ocean will be impacted. However, the drivers of organic carbon transfer are largely unknown across this region. We characterized seasonal dissolved organic carbon (DOC) concentration and dissolved organic matter (DOM) composition of WSL rivers from the middle reaches of the Ob’ River in the permafrost‐free zone, as well as tributaries of the Taz River in the northern continuous permafrost zone. DOC and aromatic DOM properties increased from spring to autumn in the Ob’ tributaries, reflecting the seasonal transition from groundwater‐sourced to terrestrial DOM. Differences in molecular‐level signatures via ultra‐high resolution mass spectrometry revealed the influence of redox processes on DOM composition in the winter while terrestrial DOM sourcing shifted from surface litter aliphatics and highly unsaturated and phenolic high‐O/C (HUP High O/C ) compounds in the spring to subsurface soils and HUP Low O/C compounds by autumn. Furthermore, aromaticity and organic N were related to landscape properties including peatlands, forest cover, and the ratio of needleleaf:broadleaf forests. Finally, the Taz River tributaries were similar to summer and autumn Ob’ tributaries, but more enriched in N and S‐containing compounds. These signatures were likely derived from thawing permafrost, which we expect to increase in northern rivers due to active layer expansion in a warming Arctic.