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Sulfate ( S O 4 2 - ) and nitrate ( N O 3 - ) account for half of the fine particulate matter mass over the eastern United States. Their wintertime concentrations have changed little in the past decade despite considerable precursor emissions reductions. The reasons for this have remained unclear because detailed observations to constrain the wintertime gas–particle chemical system have been lacking. We use extensive airborne observations over the eastern United States from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign; ground-based observations; and the GEOS-Chem chemical transport model to determine the controls on winter S O 4 2 - and N O 3 - . GEOS-Chem reproduces observed S O 4 2 - – N O 3 - – N H 4 + particulate concentrations (2.45 μg s m - 3 ) and composition ( S O 4 2 - : 47%; N O 3 - : 32%; N H 4 + : 21%) during WINTER. Only 18% of S O 2 emissions were regionally oxidized to S O 4 2 - during WINTER, limited by low [H2O2] and [OH]. Relatively acidic fine particulates (pH∼1.3) allow 45% of nitrate to partition to the particle phase. Using GEOS-Chem, we examine the impact of the 58% decrease in winter S O 2 emissions from 2007 to 2015 and find that the H2O2 limitation on S O 2 oxidation weakened, which increased the fraction of S O 2 emissions oxidizing to S O 4 2 - . Simultaneously, NOx emissions decreased by 35%, but the modeled N O 3 - particle fraction increased as fine particle acidity decreased. These feedbacks resulted in a 40% decrease of modeled [ S O 4 2 - ] and no change in [ N O 3 - ], as observed. Wintertime [ S O 4 2 - ] and [ N O 3 - ] are expected to change slowly between 2015 and 2023, unless S O 2 and NOx emissions decrease faster in the future than in the recent past.

Atmospheric emissions from the Chicago/Gary urban/industrial area significantly enhance ambient mercury (Hg) concentrations and lead to increased levels of atmospheric Hg deposition within the Lake Michigan Basin. We use airborne observations collected over Lake Michigan during the 2013 Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources, and Sinks (NOMADSS) campaign to quantify the outflow of total Hg (THg) emissions from the Chicago/Gary urban/industrial area. We use concurrent airborne measurements of THg, carbon monoxide (CO), nitrogen oxides (NOx = NO + NO2), and sulfur dioxide (SO2) to calculate measured enhancement ratios and to characterize Chicago/Gary emissions with respect to the 2011 U.S. EPA National Emissions Inventory. We determine the observed THg/CO enhancement ratio in outflow from Chicago/Gary to be 0.21 ± 0.09 × 10−6 mol mol−1 (ppqv/ppbv), which is comparable to observations reported for other major U.S. urban/industrial areas. We also employ the FLEXPART Lagrangian transport and dispersion model to simulate air mass transport during plume encounters and to compare our observations to inventoried emission ratios. We find that our observed THg/CO enhancement ratios are 63–67% greater than the transport-corrected emission ratios for the Chicago/Gary area. Our results suggest that there are many small emission sources that are not fully accounted for within the inventory, and/or that the re-emission of legacy Hg is a significant source of THg to the atmosphere in this region.

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.

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.