Abstract
Abstract. Atmospheric mercury depletion events (AMDEs) refer to a recurring depletion of mercury occurring in the springtime Arctic (and Antarctic) boundary layer, in general, concurrently with ozone depletion events (ODEs). To close some of the knowledge gaps in the physical and chemical mechanisms of AMDEs and ODEs, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents throughout porous snowpack and in the overlying atmospheric boundary layer (ABL). This paper constitutes Part 2 of the study, describing the mercury component of the model and its application to the simulation of AMDEs. Building on model components reported in Part 1 ("In-snow bromine activation and its impact on ozone"), we have developed a chemical mechanism for the redox reactions of mercury in the gas and aqueous phases with temperature dependent reaction rates and equilibrium constants accounted for wherever possible. Thus the model allows us to study the chemical and physical processes taking place during ODEs and AMDEs within a single framework where two-way interactions between the snowpack and the atmosphere are simulated in a detailed, process-oriented manner. Model runs are conducted for meteorological and chemical conditions that represent the springtime Arctic ABL characterized by the presence of "haze" (sulfate aerosols) and the saline snowpack on sea ice. The oxidation of gaseous elemental mercury (GEM) is initiated via reaction with Br-atom to form HgBr, followed by competitions between its thermal decomposition and further reactions to give thermally stable Hg(II) products. To shed light on uncertain kinetics and mechanisms of this multi-step oxidation process, we have tested different combinations of their rate constants based on published laboratory and quantum mechanical studies. For some combinations of the rate constants, the model simulates roughly linear relationships between the gaseous mercury and ozone concentrations as observed during AMDEs/ODEs by including the reaction HgBr + BrO and assuming its rate constant to be the same as for the reaction HgBr + Br, while for other combinations the results are more realistic by neglecting the reaction HgBr + BrO. Speciation of gaseous oxidized mercury (GOM) changes significantly depending on whether or not BrO is assumed to react with HgBr to form Hg(OBr)Br. Similarly to ozone (reported in Part 1), GEM is depleted via bromine radical chemistry more vigorously in the snowpack interstitial air than in the ambient air. However, the impact of such in-snow sink of GEM is found to be often masked by the re-emissions of GEM from the snow following the photo-reduction of Hg(II) deposited from the atmosphere. GOM formed in the ambient air is found to undergo fast "dry deposition" to the snowpack by being trapped on the snow grains in the top ~1 mm layer. We hypothesize that liquid-like layers on the surface of snow grains are connected to create a network throughout the snowpack, thereby facilitating the vertical diffusion of trace constituents trapped on the snow grains at much greater rates than one would expect inside solid ice crystals. Nonetheless, on the timescale of a week simulated in this study, the signal of atmospheric deposition does not extend notably below the top 1 cm of the snowpack. We propose and show that particulate-bound mercury (PBM) is produced mainly as HgBr42− by taking up GOM into bromide-enriched aerosols after ozone is significantly depleted in the air mass. In the Arctic, "haze" aerosols may thus retain PBM in ozone-depleted air masses, allowing the airborne transport of oxidized mercury from the area of its production farther than in the form of GOM. Temperature dependence of thermodynamic constants calculated in this study for Henry's law and aqueous-phase halide complex formation of Hg(II) species is a critical factor for this proposition, calling for experimental verification. The proposed mechanism may explain observed changes in the GOM–PBM partitioning with seasons, air temperature and the concurrent progress of ozone depletion in the high Arctic. The net deposition of mercury to the surface snow is shown to increase with the thickness of the turbulent ABL and to correspond well with the column amount of BrO in the atmosphere.
Highlights
Dynamic exchange of halogens between ocean, sea ice, snowpack, and atmosphere is the main driver for the frequent occurrence of ozone depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in the springtime polar boundary layer (Simpson et al, 2007; Steffen et al, 2008)
This paper constitutes Part 2 of the study, in which we investigate potential key steps leading to the net oxidation of gaseous elemental mercury (GEM) in the atmospheric boundary layer (ABL) and the snowpack interstitial air (SIA) during AMDEs, and the fate of oxidized mercury in the ABL, in the SIA and on the surface of snow grains within the snowpack
The maxima of atmospheric BrO mixing ratios simulated in these runs are in the same range as measured previously in the springtime Arctic boundary layer (Tuckermann et al, 1997; Pöhler et al, 2010; Liao et al, 2011)
Summary
Dynamic exchange of halogens between ocean, sea ice, snowpack, and atmosphere is the main driver for the frequent occurrence of ozone depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in the springtime polar boundary layer (Simpson et al, 2007; Steffen et al, 2008). Field measurements of mercury in the snowpack and overlying ambient air, including but not limited to those in the polar region, quite often indicate the photoreduction of deposited oxidized mercury back to GEM and its revolatilization to the air on timescales of days to weeks (Lalonde et al, 2002, 2003; Steffen et al, 2002; Ariya et al, 2004; Kirk et al, 2006; Johnson et al, 2008) This raises a question as to how much of the mercury deposited during the AMDEs may remain in the snowpack until snowmelt when mercury contaminating the snow could enter aquatic food chains. To some extent, the mechanism of mercury redox reactions and their rate constants are empirically defined to simulate AMDEs realistically in current 3-D models This practice is justified because of our present lack of a solid understanding of the chemical and physical mechanisms for reactive halogen release into the polar boundary layer (Abbatt et al, 2012) and of the reemission of deposited mercury as noted earlier. A potential link is indicated for the first time between the GOM–PBM partitioning during AMDEs and the partitioning of inorganic bromine changing concurrently with the depletion of ozone
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