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We use measurements made onboard the National Science Foundation's 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.

Chlorine radicals can function as a strong atmospheric oxidant, particularly in polar regions, where levels of hydroxyl radicals are low. In the atmosphere, chlorine radicals expedite the degradation of methane and tropospheric ozone, and the oxidation of mercury to more toxic forms. Here we present direct measurements of molecular chlorine levels in the Arctic marine boundary layer in Barrow, Alaska, collected in the spring of 2009 over a six-week period using chemical ionization mass spectrometry. We report high levels of molecular chlorine, of up to 400 pptv. Concentrations peaked in the early morning and late afternoon, and fell to near-zero levels at night. Average daytime molecular chlorine levels were correlated with ozone concentrations, suggesting that sunlight and ozone are required for molecular chlorine formation. Using a time-dependent box model, we estimate that the chlorine radicals produced from the photolysis of molecular chlorine oxidized more methane than hydroxyl radicals, on average, and enhanced the abundance of short-lived peroxy radicals. Elevated hydroperoxyl radical levels, in turn, promoted the formation of hypobromous acid, which catalyses mercury oxidation and the breakdown of tropospheric ozone. We therefore suggest that molecular chlorine exerts a significant effect on the atmospheric chemistry of the Arctic. [ABSTRACT FROM AUTHOR]