Thawing permafrost releases labile organic carbon and alters groundwater geochemistry and hydrology with uncertain outcomes for the mobility of hazardous metal(loid)s. Managing water quality in thawing permafrost regions is predicated on a detailed understanding of the speciation and abundance of metal(loid)s in permafrost soils and porewaters produced during thaw, which remains limited at present. This study contributes new knowledge on the sources and fate of arsenic during the thaw of organic-rich permafrost using samples collected from a subarctic permafrost region associated with geogenic arsenic (Dawson Range, Yukon, Canada). Several permafrost cores and active-layer samples from this region were analyzed for their solid-phase and aqueous geochemical characteristics and their arsenic speciation. Porewaters were extracted from permafrost cores after thaw under anaerobic conditions for aqueous geochemical analyses. Bedrock samples from the field site were also analyzed for arsenic speciation and mineralogy. X-ray diffraction and X-ray near-edge spectroscopy (XANES) analyses of weathered bedrock upgradient of soil sampling locations contained arsenic(V) hosted in iron-(oxyhydr)oxides and scorodite. XANES and micro X-ray fluorescence analyses of permafrost soils indicated a mixture of arsenic(III) and arsenic(V), indicating redox recycling of arsenic. Soil-bound arsenic was colocated with iron, likely as arseniferous iron-(oxyhydr)oxides that have been encapsulated by aggrading permafrost over geologic time. However, permafrost thaw produced porewater containing elevated dissolved arsenic (median 40 μg L–1, range 2–96 μg L–1). Thawed permafrost porewater also contained elevated dissolved iron (median 5.5 mg L–1, range 0.5–40 mg L–1) and dissolved organic carbon (median 423 mg L–1, range 72–3240 mg L–1), indicative of reducing conditions. This study highlights that arsenic can be found in reactive forms in permafrost soil, and that its thaw can release arsenic and iron to porewater and produce poor water quality.

With ongoing global warming and permafrost thawing, weathering processes will change on the Yukon River, with risks for water quality and ecosystem sustainability. Here, we explore the relationship between weathering processes and permafrost cover using elemental concentration and strontium and lithium isotopic data in the dissolved load of 102 samples collected during the summer across most major tributaries of the Yukon River. The Yukon River basin is dominated by silicate weathering with a high contribution from young volcanic rock units. In glaciated mountainous zones, we observe higher carbonate weathering contribution, low Li/Na ratios and low δ 7 Li values (<15‰). In these areas, the high denudation rate and high supply of fresh minerals associated with alpine glaciers favor congruent silicate weathering, and sulfide oxidation accelerates carbonate weathering. In floodplains covered by continuous permafrost, we observe a high carbonate weathering contribution, relatively high Li/Na ratios, and low δ 7 Li values (∼18‰). We argue that the minimal water–rock interactions in this setting inhibit silicate weathering and favor congruent weathering of easily weatherable minerals (i.e., carbonates). Conversely, in areas with discontinuous or sporadic permafrost, we observe a dominance of silicate weathering, with higher and more variable Li/Na ratios and high δ 7 Li values (11–33‰). In this setting, longer water–rock interactions combined with the high supply of fresh minerals from mountain zones favor more incongruent weathering. The unique history of Pleistocene glaciations on the Yukon River basin also influences weathering processes. Many areas of the basin were never glaciated during the Pleistocene, and rivers draining those regions have higher δ 7 Li values suggesting more incongruent weathering associated with deeper flow paths and longer water residence time in the regolith. Our work underlines that water–rock interactions, including active layer weathering and groundwater inputs, are highly dependent on climate conditions and glacial processes across the Yukon River basin, with key implications for future water quality in this warming basin.

Uranium (U) contamination in groundwater from geogenic sources affects water quality globally. Here, we use a multifaceted isotopic and geochemical approach to elucidate U sources and controls on g...

Uranium (U) contamination in groundwater from geogenic sources affects water quality globally. Here, we use a multifaceted isotopic and geochemical approach to elucidate U sources and controls on g...