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.

The impacts of Pleistocene glaciation on groundwater flow systems in sedimentary basins are widely recognized, but the timing and distribution of subglacial recharge events remain poorly constrained. We investigate the spatial and temporal variability of recharge events from glaciations over the last 2 million years in the Williston Basin, Canada. Integration of fluid chemistry, stable isotope data, and transport modeling indicate that meltwater arrived at depths of ∼600–1000 m in the northcentral region of the Williston Basin at two separate time periods, 75–150 and 300 ka, which we attribute to permeability differences between stacked aquifer systems. Our findings indicate that meltwater recharge extended along the northern margin of the Williston Basin as well as previously identified recharge areas to the east. Given the distance of measurements from recharge areas, evidence of recharge from the early to mid-Pleistocene appears to be preserved in the Williston Basin.

The impacts of Pleistocene glaciation on groundwater flow systems in sedimentary basins are widely recognized, but the timing and distribution of subglacial recharge events remain poorly constrained. We investigate the spatial and temporal variability of recharge events from glaciations over the last 2 million years in the Williston Basin, Canada. Integration of fluid chemistry, stable isotope data, and transport modeling indicate that meltwater arrived at depths of ∼600–1000 m in the northcentral region of the Williston Basin at two separate time periods, 75–150 and 300 ka, which we attribute to permeability differences between stacked aquifer systems. Our findings indicate that meltwater recharge extended along the northern margin of the Williston Basin as well as previously identified recharge areas to the east. Given the distance of measurements from recharge areas, evidence of recharge from the early to mid-Pleistocene appears to be preserved in the Williston Basin.

Brines are commonly found at depth in sedimentary basins. Many of these brines are known to be connate waters that have persisted since the early Paleozoic Era. Yet questions remain about their distribution and mechanisms for retention at depth in the Earth's crust. Here we demonstrate that there is insufficient topography to drive these dense fluids from the bottom of deep sedimentary basins. Our assessment based on driving force ratio indicates that sedimentary basins with driving force ratio > 1 contain connate waters and frequently host large evaporite deposits. These stagnant conditions appear to be relatively stable over geological time and insensitive to factors such as glaciations, erosion, compaction, and hydrocarbon generation.