Large rivers are major contributors of mercury (Hg) fluxes to the ocean, as they integrate processes of loading and loss occurring at the watershed level. Stream‐scale studies have revealed that specific landscape properties, such as wetlands or lakes, are hotspots for Hg and methylmercury (MeHg) loading, sinks and transformation, but we still do not know how they operate at the whole network scale and over large geographic gradients. In this study, we evaluate how landscape metrics are related to riverine concentrations and yields of total Hg and MeHg in 18 large boreal rivers draining watersheds ranging from 44 to 209,453 km2, distributed along a 650 km latitudinal transect in the James Bay region of Québec. Our analyses of landscape metrics using elastic net models and mixed models reinforce the role of wetlands as sources of MeHg, but further show that surface coverage of water in the watershed is the major driver of both Hg and MeHg concentrations and fluxes at the whole network scale. Our findings also demonstrate that seasonality modulates the relationship between landscape properties and Hg forms. Based on hydrologic data, we additionally estimate annual fluxes for the whole Eastern James Bay to 441 kg Hg and 14.6 kg MeHg, and average landscape yield to 1.24 g Hg km−2 y−1 and 0.041 g MeHg km−2 y−1. Our study provides tools to broadly predict riverine Hg concentrations and fluxes with only a few easily accessible landscape metrics, which were shown to be better predictors than physico‐chemical variables.

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Co‐loading of mercury (Hg) with dissolved organic carbon (DOC) is a key driver of the observed spatial and temporal Hg patterns among aquatic ecosystems. Their strong biogeochemical coupling has spurred the use of DOC as a predictor of Hg concentrations and exports in boreal regions where sampling logistics for Hg are costly and complex. Yet relationships between Hg and methylmercury (MeHg) with DOC have recently been shown to be highly variable in terms of slope and strength, suggesting that mechanisms other than co‐transport along the land‐water continuum may drive the relationship between Hg and DOC across landscapes. In this study, we explore the relationship between Hg and MeHg with DOC across 18 boreal rivers collectively draining over 350,000 km2 of the eastern James Bay territory (Québec), comprising watersheds with a wide range of vegetation, water residence time and riverine DOC concentrations and optical properties. Our results show that although a large portion of the variation in Hg and MeHg is explained by concentrations of DOC, Hg‐DOC and MeHg‐DOC relationships and ratios vary greatly both spatially and temporally. We show that ratios and strength of the coupling can be predicted from system hydrology, with declines in Hg:DOC and increase in MeHg:DOC ratios and stronger coupling during the seasonal progression to warmer temperatures, higher water evaporation, and longer residence time. Our study highlights the role of seasonal hydrology and biogeochemical processing in governing Hg, MeHg and DOC patterns in boreal rivers.