[en] Highlights: • A small catchment lake preserves mercury isotopic signatures in sediments. • Atmospheric mercury deposition has increased 4-fold since 1850. • MDF and odd-MIF increase since 1850, reflecting increased photochemical reduction. -- Abstract: Mercury (Hg) deposition from the atmosphere has increased dramatically since 1850 and Hg isotope records in lake sediments can be used to identify changes in the sources and cycling of Hg. We collected a sediment core from a remote lake (Lost Lake, Wyoming, USA) and measured vertical variation of Hg concentration and isotopic composition as well as ²¹⁰Pb and ¹³⁷Cs activities to establish a chronology. We also analyzed vegetation and soil samples from the watershed which has a small ratio of watershed area to lake surface area (2.06). The Hg flux remains constant from ~1350 to 1850 before increasing steadily to modern values that are approximately four times pre-1850 values. The modern Hg isotopic composition preserved in the sediments is distinct from the Hg isotopic composition of pre-1850 samples with both δ²⁰²Hg and Δ¹⁹⁹Hg becoming progressively more positive through time, with shifts of +0.37‰ and +0.23‰ respectively. To explain temporal changes in δ²⁰²Hg, Δ¹⁹⁹Hg, and Hg concentration in the core segments, we estimated a present-day atmospheric endmember based on precipitation and snow samples collected near Lost Lake. The observed change in Hg isotopic values through time cannot be explained solely by addition of anthropogenic Hg with the isotopic composition that has been estimated by others for global anthropogenic emissions. Instead, the isotope variation suggests that the relative importance of redox transformations, whether in the atmosphere, within the lake, or both, have changed since 1850.

[en] Highlights: • Contrasting atmospheric processes control the Hg isotopic composition in snow. • Polar vortex snow progresses towards more negative odd-MIF when aged in sunlight. • Photoreduction of Hg(II) drives odd-MIF in mid-latitude snow. • Isotopic analysis of snowmelt is important for ecosystem Hg source identification. Atmospheric deposition of mercury (Hg) to terrestrial and aquatic ecosystems has significant implications for human and animal exposure. Measurements of Hg isotopic composition can be utilized to trace sources of Hg, but outside of the Arctic there has been little Hg isotopic characterization of snow. To better understand deposition pathways at mid-latitudes, five time series of snowfall were collected at two sites (Dexter and Pellston, Michigan, USA) to investigate the Hg isotopic composition of snowfall, how it changes after deposition, and how it compares to rain. The Hg isotopic composition of a subset of fresh snow samples revealed the influence of reactive surface uptake of atmospheric Hg(0). The first time series collected at Dexter occurred during a polar vortex, demonstrating Hg isotopic fractionation dynamics similar to those in Arctic snow, with increasingly negative Δ¹⁹⁹Hg as snow aged with exposure to sunlight. All other time series revealed an increase in Δ¹⁹⁹Hg as snow aged, with values reaching up to 3.5‰. This characterization of Hg isotopes in snow suggests a strong influence of oxidants and binding ligands in snow that may mediate Hg isotope fractionation. Additionally, isotopic characterization of Hg in snow deposited to natural ecosystems at mid-latitudes allows for better understanding of atmospheric mercury sources that are deposited to lakes and forests and that may become available for methylation and transfer to food webs.