Contrasting Controls on the Diel Isotopic Variation of Hg0 at Two High Elevation Sites in the Western United States.

The atmosphere is a significant global reservoir for mercury (Hg) and its isotopic characterization is important to understand sources, distribution, and deposition of Hg to the Earth's surface. To better understand Hg isotope variability in the remote background atmosphere, we collected continuous 12-h Hg0 samples for 1 week from two high elevation sites, Camp Davis, Wyoming (valley), and Mount Bachelor, Oregon (mountaintop). The samples collected at Camp Davis displayed strong diel variation in δ202Hg values of Hg0, but not in Δ199Hg or Δ200Hg values. We attribute this pattern to nightly atmospheric inversions trapping Hg in the valley and the subsequent nighttime uptake of Hg by vegetation, which depletes Hg from the atmosphere. At Mount Bachelor, the samples displayed diel variation in both δ202Hg and Δ199Hg, but not Δ200Hg. We attribute this pattern to differences in the vertical distribution of Hg in the atmosphere as Mount Bachelor received free tropospheric air masses on certain nights during the sampling period. Near the end of the sampling period at Mount Bachelor, the observed diel pattern dissipated due to the influence of a nearby forest fire. The processes governing the Hg isotopic fractionation differ across sites depending on mixing, topography, and vegetation cover.

Isotopic Characterization of Mercury Downstream of Historic Industrial Contamination in the South River, Virginia.

Historic point source mercury (Hg) contamination from industrial processes on the South River (Waynesboro, Virginia) ended decades ago, but elevated Hg concentrations persist in the river system. In an effort to better understand Hg sources, mobility, and transport in the South River, we analyzed total Hg (THg) concentrations and Hg stable isotope compositions of streambed sediments, stream bank soils, suspended particles, and filtered surface waters. Samples were collected along a longitudinal transect of the South River, starting upstream of the historic Hg contamination point-source and extending downstream to the confluence with the South Fork Shenandoah River. Analysis of the THg concentration and Hg isotopic composition of these environmental samples indicates that the regional background Hg source is isotopically distinct in both Δ199Hg and δ202Hg from Hg derived from the original source of contamination, allowing the tracing of contamination-sourced Hg throughout the study reach. Three distinct end-members are required to explain the Hg isotopic and concentration variation observed in the South River. A consistent negative offset in δ202Hg values (∼0.28‰) was observed between Hg in the suspended particulate and dissolved phases, and this fractionation provides insight into the processes governing partitioning and transport of Hg in this contaminated river system.

Isotopic composition of mercury deposited via snow into mid-latitude ecosystems.

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.

Changes in the mercury isotopic composition of sediments from a remote alpine lake in Wyoming, USA.

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.

Biogenic carbonate mercury and marine temperature records reveal global influence of Late Cretaceous Deccan Traps.

The climate and environmental significance of the Deccan Traps large igneous province of west-central India has been the subject of debate in paleontological communities. Nearly one million years of semi-continuous Deccan eruptive activity spanned the Cretaceous-Paleogene boundary, which is renowned for the extinction of most dinosaur groups. Whereas the Chicxulub impactor is acknowledged as the principal cause of these extinctions, the Deccan Traps eruptions are believed to have contributed to extinction patterns and/or enhanced ecological pressures on biota during this interval of geologic time. We present the first coupled records of biogenic carbonate clumped isotope paleothermometry and mercury concentrations as measured from a broad geographic distribution of marine mollusk fossils. These fossils preserve evidence of simultaneous increases in coastal marine temperatures and mercury concentrations at a global scale, which appear attributable to volcanic CO2 and mercury emissions. These early findings warrant further investigation with additional records of combined Late Cretaceous temperatures and mercury concentrations of biogenic carbonate.