Comparison of arsenic and molybdenum geochemistry in meromictic lakes of the McMurdo Dry Valleys, Antarctica: Implications for oxyanion-forming trace element behavior in permanently stratified lakes

• As and Mo concentrations are compared in meromictic Antarctic lakes.
• Weathering in catchment basins is chief supplier of As and Mo to these lakes.
• Biogeochemical cycling of As appears to be important in these lakes.
• Modeling suggests As and Mo thioanions form in anoxic monimolimnions.
• Thioanions stabilize As in solution but promote Mo removal to sediments.

Water samples were collected for arsenic (As) and molybdenum (Mo) analysis from different depths in Lakes Hoare and Fryxell, both of which are located in the Taylor Valley within the McMurdo Dry Valleys of Antarctica. Sampling depths within each lake were chosen to capture variations in As and Mo concentrations and As speciation in the oxic mixolimnia and anoxic monimolimnia of these meromictic lakes. Arsenic concentrations ranged from 0.67 nmol kg− 1 to 3.54 nmol kg− 1 in Lake Hoare and from 1.69 nmol kg− 1 to 17.5 nmol kg− 1 in Lake Fryxell. Molybdenum concentrations varied between 5.05 nmol kg− 1 and 43 nmol kg− 1 in Lake Hoare, and between 3.52 nmol kg− 1 and 25.5 nmol kg− 1 in Lake Fryxell. Concentrations of As and Mo generally increased with depth in the mixolimnion of each lake, consistent with uptake near the ice–water interface by organic particles and/or Fe/Mn oxides/oxyhydroxides, followed by gravitational settling and regeneration/remineralization at depth in the vicinity of the redoxcline. Arsenic concentrations either remained constant (Hoare) or increased with depth (Fryxell) in the anoxic monimolimnia, whereas Mo exhibited dramatic decreases in concentrations across the redoxcline in both lakes. Geochemical modeling predicts that As and Mo occur as thioanions in the anoxic bottom waters of Lakes Hoare and Fryxell, and further that the contrasting behavior of both trace elements reflects the respective reactivity of their thioanions towards Fe-sulfide minerals such as mackinawite (FeS) and/or pyrite (FeS2). More specifically, the geochemical model suggests that Fe-sulfide mineral precipitation in the anoxic monimolimnia of both lakes regulates dissolved sulfide concentrations at levels that are too low for As-sulfide minerals (e.g., orpiment, realgar) to precipitate, whereas mackinawite and/or pyrite react(s) with particle reactive thiomolybdate anions, possibly forming an Fe–Mo–S mineral that precipitates and, hence, leads to Mo removal from solution.