Lynne E. Gratz

Isotopic Composition and Fractionation of Mercury in Great Lakes Precipitation and Ambient Air

Atmospheric deposition is a primary pathway by which mercury (Hg) enters terrestrial and aquatic ecosystems; however, the chemical and meteorological processes that Hg undergoes from emission to deposition are not well understood. Hg stable isotope geochemistry is a growing field used to better understand Hg biogeochemical cycling. To examine the atmospheric Hg isotopic composition in the Great Lakes, precipitation and ambient vapor-phase Hg samples were collected in Chicago, IL, Holland, MI, and Dexter, MI, between April 2007 and September 2009. Precipitation samples were characterized by negative mass-dependent fractionation (MDF) (δ(202)Hg = -0.79‰ to 0.18‰), while most vapor-phase samples displayed positive MDF (δ(202)Hg = -0.59‰ to 0.43‰). Positive mass-independent fractionation (MIF) (Δ(199)Hg = 0.04‰ to 0.52‰) was observed in precipitation, whereas MIF was slightly negative in vapor-phase samples (Δ(199)Hg = -0.21‰ to 0.06‰). Significant positive MIF of (200)Hg up to 0.25‰ was also measured in precipitation. Such MIF of an even-mass Hg isotope has not been previously reported in natural samples. These results contrast with recent predictions of the isotopic composition of atmospheric Hg and suggest that, in addition to aqueous photoreduction, other atmospheric redox reactions and source-related processes may contribute to isotopic fractionation of atmospheric Hg.

Oxidation of mercury by bromine in the subtropical Pacific free troposphere

Mercury is a global toxin that can be introduced to ecosystems through atmospheric deposition. Mercury oxidation is thought to occur in the free troposphere by bromine radicals, but direct observational evidence for this process is currently unavailable. During the 2013 Nitrogen, Oxidants, Mercury and Aerosol Distributions, Sources and Sinks campaign, we measured enhanced oxidized mercury and bromine monoxide in a free tropospheric air mass over Texas. We use trace gas measurements, air mass back trajectories, and a chemical box model to confirm the origin and chemical history of the sampled air mass. We find the presence of elevated oxidized mercury to be consistent with oxidation of elemental mercury by bromine atoms in this subsiding upper tropospheric air mass within the subtropical Pacific High, where dry atmospheric conditions are conducive to oxidized mercury accumulation. Our results support the role of bromine as the dominant oxidant of mercury in the upper troposphere.

Mercury Emission Ratios from Coal-Fired Power Plants in the Southeastern United States during NOMADSS

We use measurements made onboard the National Science Foundations C-130 research aircraft during the 2013 Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) experiment to examine total Hg (THg) emission ratios (EmRs) for six coal-fired power plants (CFPPs) in the southeastern U.S. We compare observed enhancement ratios (ERs) with EmRs calculated using Hg emissions data from two inventories: the National Emissions Inventory (NEI) and the Toxics Release Inventory (TRI). For four CFPPs, our measured ERs are strongly correlated with EmRs based on the 2011 NEI (r(2) = 0.97), although the inventory data exhibit a -39% low bias. Our measurements agree best (to within ±32%) with the NEI Hg data when the latter were derived from on-site emissions measurements. Conversely, the NEI underestimates by approximately 1 order of magnitude the ERs we measured for one previously untested CFPP. Measured ERs are uncorrelated with values based on the 2013 TRI, which also tends to be biased low. Our results suggest that the Hg inventories can be improved by targeting CFPPs for which the NEI- and TRI-based EmRs have significant disagreements. We recommend that future versions of the Hg inventories should provide greater traceability and uncertainty estimates.