Ecohydrological and geological controls on contaminant reservoirs in degrading permafrost peatlands

Peatlands are important sinks and/or sources of carbon, solutes, and elements of potential concern (e.g., Hg, As, Pb, Cu, Zn) to their surrounding environments. Minerogenic permafrost peatlands that receive input of elements from groundwater and weathering of bedrock and surficial materials accumulate substantial amounts of geogenic-derived elements over millennia, which are then frozen in place. As the Arctic cryosphere thaws due to 21^st. c climate warming, understanding of permafrost contaminant reservoirs and tracking their release is a growing challenge due to a lack of knowledge on the cumulative and interacting influences of bedrock and surficial geology, vegetation, climate, fire, and ecohydrology on contaminant accumulation in permafrost peatlands. We examined the Holocene history of two permafrost peatlands from the Northwest Territories, Canada, that are underlain by mineralized volcanic and metasedimentary (Daigle Lake peatland) and unmineralized granitoid (Handle Lake peatland) bedrock. Laboratory methods included pyrolytic speciation to determine the quality and quantity of solid organic matter; plant macrofossil and macroscopic charcoal analysis to reconstruct vegetation, peatland development, and fire history; testate amoebae to reconstruct paleohydrological conditions; and inorganic geochemical analyses to determine elemental concentration over time. Both sites have undergone several marked and broadly coincident hydrological shifts and phases of ecohydrological development. During the early Holocene (ca. 8000-5000 cal BP) initial shallow lake environments at both sites transitioned to rich fen and were colonized by Picea. Elevated concentrations of Zn (up to 65 mg^.kg^-1), Cu (up to 52 mg^.kg^-1), As (up to 140 mg^.kg-1), and Cr (up to 65 mg^.kg^-1) occur in the basal lacustrine sediments, particularly at the Daigle Lake peatland that is underlain by mineralized bedrock, but become lower in overlying material that accumulated in a fen setting. Depth to water table increased by almost 30 cm in the Handle Lake peatland between ca. 5900 and 4900 cal BP, coincident with the Holocene Thermal Maximum. At this time, local fires were severe and frequent at both sites and associated with elevated Hg (up to 50 µg^.kg^-1) in the peat. After this dry interval, the water table rose at ca. 3000 cal BP at the Handle Lake peatland and by ca. 2200 cal BP at the Daigle Lake peatland. Fire occurrence declined, coincident with the relatively cool and wet conditions of the Neoglacial interval. A bog was established at both sites between ca. 2700 and 2200 cal BP. Fire occurrence and the concentration of Hg (up to 175 µg^.kg^-1), As (up to 300 mg^.kg^-1), and Zn (up to 50 mg^.kg^-1) have increased over the past 1000 cal yrs, likely due to a combination of anthropogenic input of As and Hg associated with gold mining in the region and global industrialization as well as warming climate and permafrost thaw. This study illustrates the influence of ecohydrology and bedrock geology on the chemical stores of permafrost peatlands.