Mercury (Hg) is a critical environmental concern. Although an important component of its biogeochemical cycle, large uncertainties still exist in the estimates of surface fluxes of mercury. Three projects presented in this thesis improve our understanding of mercury surface fluxes at different spatial scales by combining atmospheric observations and models. First, a global scale inverse model study uses observations at multiple ground-based stations and simulations from a three-dimensional chemical transport model (GEOS-Chem) to obtain a total mercury emission of about 5.8 Gg yr⁰ (gaseous elemental mercury). The optimized Asian anthropogenic emissions (0.7-1.8 Gg yr⁰. The inversion also suggests that the legacy mercury releases tend to reside in the terrestrial system rather than in the ocean. Second, the comparison of nested grid GEOS-Chem model simulations with aircraft observations support results from the global inversion, and further suggests that the Northwest Atlantic Ocean is a net source of Hg⁰, with high evasion fluxes in summer (related to the high precipitation rates and deposition fluxes of oxidized mercury), whereas the terrestrial ecosystem in the eastern United States is likely a net sink of Hg⁰ during summer. Third, a one-dimensional chemical transport model is built and used to simulate the mercury diurnal variabilities observed at Dome Concordia on the Antarctic plateau. The model simulation best reproducing the Hg⁰ observations shows that in summer mercury is rapidly cycled between the shallow atmospheric boundary layer and the surface snowpack. A two-step bromine initiated scheme oxidizes Hg⁰. Oxidized mercury is deposited, photoreduced in the surface snow, and reemitted as Hg⁰ back into the atmosphere.

We infer global and regional emissions of five of the most abundant hydrofluorocarbons (HFCs) using atmospheric measurements from the Advanced Global Atmospheric Gases Experiment and the National Institute for Environmental Studies, Japan, networks. We find that the total CO₂-equivalent emissions of the five HFCs from countries that are required to provide detailed, annual reports to the United Nations Framework Convention on Climate Change (UNFCCC) increased from 198 (175–221) Tg-CO₂-eq⋅y^–1 in 2007 to 275 (246–304) Tg-CO₂-eq⋅y^–1 in 2012. These global warming potential-weighted aggregated emissions agree well with those reported to the UNFCCC throughout this period and indicate that the gap between reported emissions and global HFC emissions derived from atmospheric trends is almost entirely due to emissions from nonreporting countries. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63–95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.

© 2015 National Academy of Sciences

We describe a new 4D-Var inversion framework for nitrous oxide (N₂O) based on the GEOS-Chem chemical transport model and its adjoint, and apply it in a series of observing system simulation experiments to assess how well N₂O sources and sinks can be constrained by the current global observing network. The employed measurement ensemble includes approximately weekly and quasi-continuous N₂O measurements (hourly averages used) from several long-term monitoring networks, N₂O measurements collected from discrete air samples onboard a commercial aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container; CARIBIC), and quasi-continuous measurements from the airborne HIAPER Pole-to-Pole Observations (HIPPO) campaigns. For a 2-year inversion, we find that the surface and HIPPO observations can accurately resolve a uniform bias in emissions during the first year; CARIBIC data provide a somewhat weaker constraint. Variable emission errors are much more difficult to resolve given the long lifetime of N₂O, and major parts of the world lack significant constraints on the seasonal cycle of fluxes. Current observations can largely correct a global bias in the stratospheric sink of N₂O if emissions are known, but do not provide information on the temporal and spatial distribution of the sink. However, for the more realistic scenario where source and sink are both uncertain, we find that simultaneously optimizing both would require unrealistically small errors in model transport. Regardless, a bias in the magnitude of the N₂O sink would not affect the a posteriori N₂O emissions for the 2-year timescale used here, given realistic initial conditions, due to the timescale required for stratosphere–troposphere exchange (STE). The same does not apply to model errors in the rate of STE itself, which we show exerts a larger influence on the tropospheric burden of N₂O than does the chemical loss rate over short (< 3 year) timescales. We use a stochastic estimate of the inverse Hessian for the inversion to evaluate the spatial resolution of emission constraints provided by the observations, and find that significant, spatially explicit constraints can be achieved in locations near and immediately upwind of surface measurements and the HIPPO flight tracks; however, these are mostly confined to North America, Europe, and Australia. None of the current observing networks are able to provide significant spatial information on tropical N₂O emissions. There, averaging kernels (describing the sensitivity of the inversion to emissions in each grid square) are highly smeared spatially and extend even to the midlatitudes, so that tropical emissions risk being conflated with those elsewhere. For global inversions, therefore, the current lack of constraints on the tropics also places an important limit on our ability to understand extratropical emissions. Based on the error reduction statistics from the inverse Hessian, we characterize the atmospheric distribution of unconstrained N₂O, and identify regions in and downwind of South America, central Africa, and Southeast Asia where new surface or profile measurements would have the most value for reducing present uncertainty in the global N₂O budget.<

The Southern Ocean has shown little warming over recent decades, in stark contrast to the rapid warming observed in the Arctic. Along the northern flank of the Antarctic Circumpolar Current, however, the upper ocean has warmed substantially. Here we present analyses of oceanographic observations and general circulation model simulations showing that these patterns—of delayed warming south of the Antarctic Circumpolar Current and enhanced warming to the north—are fundamentally shaped by the Southern Ocean’s meridional overturning circulation: wind-driven upwelling of unmodified water from depth damps warming around Antarctica; greenhouse gas-induced surface heat uptake is largely balanced by anomalous northward heat transport associated with the equatorward flow of surface waters; and heat is preferentially stored where surface waters are subducted to the north. Further, these processes are primarily due to passive advection of the anomalous warming signal by climatological ocean currents; changes in ocean circulation are secondary. These findings suggest the Southern Ocean responds to greenhouse gas forcing on the centennial, or longer, timescale over which the deep ocean waters that are upwelled to the surface are warmed themselves. It is against this background of gradual warming that multidecadal Southern Ocean temperature trends must be understood.