scholarly journals Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 1: In-snow bromine activation and its impact on ozone

2014 ◽  
Vol 14 (8) ◽  
pp. 4101-4133 ◽  
Author(s):  
K. Toyota ◽  
J. C. McConnell ◽  
R. M. Staebler ◽  
A. P. Dastoor
Keyword(s):  
Boundary Layer ◽  
Mass Transfer ◽  
Gas Phase ◽  
Aqueous Phase ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
The Arctic ◽  
Radical Chemistry ◽  
Ozone Loss ◽  
Key Species

Abstract. To provide a theoretical framework towards a better understanding of ozone depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in the polar boundary layer, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents from porous snowpack and through the atmospheric boundary layer (ABL) as a unified system. This paper constitutes Part 1 of the study, describing a general configuration of the model and the results of simulations related to reactive bromine release from the snowpack and ODEs during the Arctic spring. A common set of aqueous-phase reactions describes chemistry both within the liquid-like layer (LLL) on the grain surface of the snowpack and within deliquesced "haze" aerosols mainly composed of sulfate in the atmosphere. Gas-phase reactions are also represented by the same mechanism in the atmosphere and in the snowpack interstitial air (SIA). Consequently, the model attains the capacity of simulating interactions between chemistry and mass transfer that become particularly intricate near the interface between the atmosphere and the snowpack. In the SIA, reactive uptake on LLL-coated snow grains and vertical mass transfer act simultaneously on gaseous HOBr, a fraction of which enters from the atmosphere while another fraction is formed via gas-phase chemistry in the SIA itself. A "bromine explosion", by which HOBr formed in the ambient air is deposited and then converted heterogeneously to Br2, is found to be a dominant process of reactive bromine formation in the top 1 mm layer of the snowpack. Deeper in the snowpack, HOBr formed within the SIA leads to an in-snow bromine explosion, but a significant fraction of Br2 is also produced via aqueous radical chemistry in the LLL on the surface of the snow grains. These top- and deeper-layer productions of Br2 both contribute to the release of Br2 to the atmosphere, but the deeper-layer production is found to be more important for the net outflux of reactive bromine. Although ozone is removed via bromine chemistry, it is also among the key species that control both the conventional and in-snow bromine explosions. On the other hand, aqueous-phase radical chemistry initiated by photolytic OH formation in the LLL is also a significant contributor to the in-snow source of Br2 and can operate without ozone, whereas the delivery of Br2 to the atmosphere becomes much smaller after ozone is depleted. Catalytic ozone loss via bromine radical chemistry occurs more rapidly in the SIA than in the ambient air, giving rise to apparent dry deposition velocities for ozone from the air to the snow on the order of 10−3 cm s−1 during daytime. Overall, however, the depletion of ozone in the system is caused predominantly by ozone loss in the ambient air. Increasing depth of the turbulent ABL under windy conditions will delay the buildup of reactive bromine and the resultant loss of ozone, while leading to the higher column amount of BrO in the atmosphere. During the Arctic spring, if moderately saline and acidic snowpack is as prevalent as assumed in our model runs on sea ice, the shallow, stable ABL under calm weather conditions may undergo persistent ODEs without substantial contributions from blowing/drifting snow and wind-pumping mechanisms, whereas the column densities of BrO in the ABL will likely remain too low in the course of such events to be detected unambiguously by satellite nadir measurements.

scholarly journals Air-snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 1: In-snow bromine activation and its impact on ozone

2013 ◽  
Vol 13 (8) ◽  
pp. 20341-20418 ◽  
Author(s):  
K. Toyota ◽  
J. C. McConnell ◽  
R. M. Staebler ◽  
A. P. Dastoor
Keyword(s):  
Boundary Layer ◽  
Aqueous Phase ◽  
Ambient Air ◽  
Atmospheric Mercury ◽  
Chemical Mechanism ◽  
The Arctic ◽  
Radical Chemistry ◽  
Ozone Loss ◽  
Key Species ◽  
Reactive Trace Gases

Abstract. To provide a theoretical framework towards better understanding of ozone depletion events (ODEs) and atmospheric mercury depletion events (AMDEs) in the polar boundary layer, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents from porous snowpack and through the atmospheric boundary layer (ABL) as a unified system. In this paper, we describe a general configuration of the model and the results of simulations related to reactive bromine release from the snowpack and ODEs during the Arctic spring. The model employs a chemical mechanism adapted from the one previously used for the simulation of multiphase halogen chemistry involving deliquesced sea-salt aerosols in the marine boundary layer. A common set of aqueous-phase reactions describe chemistry both in the liquid-like (or brine) layer on the grain surface of the snowpack and in "haze" aerosols mainly composed of sulfate in the atmosphere. The process of highly soluble/reactive trace gases, whether entering the snowpack from the atmosphere or formed via gas-phase chemistry in the snowpack interstitial air (SIA), is simulated by the uptake on brine-covered snow grains and subsequent reactions in the aqueous phase while being traveled vertically within the SIA. A "bromine explosion", by which, in a conventional definition, HOBr formed in the ambient air is deposited and then converted heterogeneously to Br2, is a dominant process of reactive bromine formation in the top 1 mm (or less) layer of the snowpack. Deeper in the snowpack, HOBr formed within the SIA leads to an in-snow bromine explosion, but a significant fraction of Br2 is also produced via aqueous radical chemistry in the brine on the surface of the snow grains. These top- and deeper-layer productions of Br2 both contribute to the Br2 release into the atmosphere, but the deeper-layer production is found to be more important for the net outflux of reactive bromine. Although ozone is removed via bromine chemistry, it is also among the key species that control both the conventional and in-snow bromine explosions. On the other hand, aqueous-phase radical chemistry initiated by photolytic OH formation in the liquid-like layer is also a significant contributor to the in-snow source of Br2 and can operate without ozone, whereas the delivery of Br2 to the atmosphere becomes much smaller after ozone is depleted. Catalytic ozone loss via bromine radicals occurs more rapidly in the SIA than in the ambient air, giving rise to apparent dry deposition velocities for ozone from the air to the snow on the order of 10−3 cm s-1 under sunlight. Overall, however, the depletion of ozone in the system is caused predominantly by ozone loss in the ambient air. Increasing depth of the turbulent ABL under windy conditions will delay the build-up of reactive bromine and the resultant loss of ozone, while leading to the higher column amount of BrO in the atmosphere. If moderately saline and acidic snowpack is as prevalent as assumed in our model runs on sea ice during the spring, the shallow, stable ABL under calm weather conditions may undergo persistent ODEs without substantial contributions from blowing/drifting snow and wind-pumping mechanisms, whereas the column densities of BrO in the ABL will likely remain too low during the course of such events to be detected unambiguously by satellite nadir measurements.

scholarly journals Air-snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 2: Mercury and its speciation

2013 ◽  
Vol 13 (8) ◽  
pp. 22151-22220 ◽  
Author(s):  
K. Toyota ◽  
A. P. Dastoor ◽  
A. Ryzhkov
Keyword(s):  
Boundary Layer ◽  
Temperature Dependence ◽  
Ozone Depletion ◽  
Ambient Air ◽  
Companion Paper ◽  
Atmospheric Mercury ◽  
Chemical Mechanism ◽  
The Arctic ◽  
Radical Chemistry ◽  
Trace Constituents

Abstract. Atmospheric mercury depletion events (AMDEs) refer to a recurring depletion of mercury in the springtime Arctic (and Antarctic) boundary layer, occurring, 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). Building on the model reported in a companion paper (Part 1: In-snow bromine activation and its impact on ozone), we have expanded the chemical mechanism to include the reactions of mercury in the gas- and aqueous-phases with temperature dependence of rate 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 representing the springtime Arctic ABL loaded with "haze" sulfate aerosols and the underlying saline snowpack laid on sea ice. Using recent updates for the Hg + Br ⇄ HgBr reaction kinetics, we show that the rate and magnitude of photochemical loss of gaseous elemental mercury (GEM) during AMDEs exhibit a strong dependence on the choice of reaction(s) of HgBr subsequent to its formation. At 253 K, the temperature that is presumably low enough for bromine radical chemistry to cause prominent AMDEs as indicated from field observations, the parallel occurrence of AMDEs and ODEs is simulated if the reaction HgBr + BrO is assumed to produce a thermally stable intermediate, Hg(OBr)Br, at the same rate constant as the reaction HgBr + Br. On the contrary, the simulated depletion of atmospheric mercury is notably diminished by not allowing the former reaction to occur in the model. Similarly to ozone (reported in the companion paper), GEM is destroyed 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. Gaseous oxidized mercury (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 few centimeters 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 a major part of changes in the GOM-PBM partitioning with seasons, air temperature and the concurrent progress of ozone depletion as observed 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.

scholarly journals Numerical Analysis of the Role of Snowpack in the Ozone Depletion Events during the Arctic Spring

2016 ◽  
Author(s):  
Le Cao ◽  
Ulrich Platt ◽  
Chenggang Wang ◽  
Nianwen Cao ◽  
Qing Qin
Keyword(s):  
Boundary Layer ◽  
Mass Transfer ◽  
Mass Exchange ◽  
Ozone Depletion ◽  
Volume Fraction ◽  
Ambient Air ◽  
The Arctic ◽  
Critical Parameters ◽  
Surface Snow ◽  
Interstitial Air

Abstract. The tropospheric ozone depletion events (ODEs) and the related enhancement of reactive bromine in the boundary layer were observed in the springtime of Arctic almost 40 years ago. It is found that various substrates in polar regions such as the snowpack are able to release bromine, which is responsible for the consumption of ozone in the boundary layer. In the present simulation, a snowpack module which represents the mass transfer between the ambient air and the snowpack is implemented in a box model, aiming to clarify the influences of the snowpack on ODEs and the associated bromine explosion in the ambient air as well as in the interstitial air of the snowpack. In the snowpack module, the processes including the deposition of bromine containing compounds onto the snowpack, the mass exchange between the snow interstitial air and snow particles, and the release of Br2 from the snowpack to the ambient air are parameterized by estimating the transfer resistances which an air parcel experiences when being transported through the boundary layer into the snowpack. The present model successfully captures the complete removal of ozone both in the boundary layer and in the snow interstitial air. The temporal and spatial distributions of bromine species such as Br2 are shown and compared with observations. By changing the properties of the snowpack, it is found that the size of snow grains, volume fraction of the liquid-like layer (LLL), and the rate of the mass exchange between the snow interstitial air and the snow particles are the critical parameters which determine the occurrence of ODEs. The simulation results show that a smaller size of the snow grains considerably accelerates the ozone depletion process. Moreover, the decrease of LLL volume fraction in snow grains is found to slow down the scavenging process of HOBr by the snow particles, which prohibits the occurrence of ODEs in the snowpack. In addition, according to the simulations with the modification of the snowpack thickness, the depletion of ozone in the ambient air is shown to be influenced more heavily by the bromine explosion occurring in the surface snow layers instead of the deep snow layers. The importance of each step in the mass transfer processes occurring between the boundary layer and the snowpack is identified by conducting a local concentration sensitivity analysis. It is shown that the snow chemistry occurring in the surface snow layers has a relatively larger impact on the depletion of ozone in the ambient air compared to that within the deep snow layers. Besides, during the period of the ozone depletion, the mixing ratio of ozone in the boundary layer is mostly influenced by the deposition of HOBr onto the surface snow layers and the release of Br2 from the snow layers close to the ground surface. In contrast to that, in the interstitial air of the surface snow layer, the uptake of HOBr by snow particles is indicated as the most dominant step for the ODE.

scholarly journals Reproducing springtime Arctic tropospheric ozone depletion events in an outdoor mesocosm sea-ice facility

2021 ◽  
Author(s):  
Zhiyuan Gao ◽  
Nicolas-Xavier Geilfus ◽  
Alfonso Saiz-Lopez ◽  
Feiyue Wang
Keyword(s):  
Boundary Layer ◽  
Sea Ice ◽  
Gas Phase ◽  
Ozone Depletion ◽  
Surface Ozone ◽  
Environmental Research ◽  
The Arctic ◽  
Ozone Loss ◽  
Ozone Concentrations ◽  
Air Temperatures

Abstract. The episodic build-up of gas-phase reactive bromine species over sea ice and snowpack in the springtime Arctic plays an important role in the boundary layer, causing annual concurrent depletion of ozone and gaseous elemental mercury during polar sunrise. Extensive studies have shown that these phenomena, known as bromine explosion events (BEEs), ozone depletion events (ODEs) and mercury depletion events (MDEs), respectively, are all triggered by gas-phase reactive bromine species that are photochemically activated from bromide via multi-phase reactions under freezing air temperatures. However, major knowledge gaps exist in both fundamental cryo-photochemical processes causing these events and meteorological conditions that may affect their timing and magnitude. Here, we report an outdoor mesocosm-scale study in which we successfully reproduced ODEs at the Sea-ice Environmental Research Facility (SERF) in Winnipeg, Canada. By monitoring ozone concentrations inside large, acrylic tubes over bromide-enriched artificial seawater during entire sea ice freeze-and-melt cycles, we observed mid-day photochemical ozone loss in winter in the boundary layer air immediately above the sea ice surface in a pattern that is characteristic of BEE-induced ODEs in the Arctic. The importance of UV radiation and the presence of a condensed phase (experimental sea ice or snow) in causing such surface ozone loss was demonstrated by comparing ozone concentrations between UV-transmitting and UV-blocking acrylic tubes under different air temperatures. The ability of reproducing BEE-induced ODEs at a mesocosm scale in a non-polar region provides a new approach to systematically studying the cryo-photochemical and meteorological processes leading to BEEs, ODEs, and MDEs in the Arctic, their role in biogeochemical cycles across the ocean-sea ice-atmosphere interfaces, and their sensitivities to climate change.

scholarly journals Polyfluoroalkyl compounds in the Canadian Arctic atmosphere

2011 ◽  
Vol 8 (4) ◽  
pp. 399 ◽  
Author(s):  
Lutz Ahrens ◽  
Mahiba Shoeib ◽  
Sabino Del Vento ◽  
Garry Codling ◽  
Crispin Halsall
Keyword(s):  
Gas Phase ◽  
Environmental Concern ◽  
Canadian Arctic ◽  
High Volume ◽  
Ambient Air ◽  
Coast Guard ◽  
The Arctic ◽  
Particle Phase ◽  
Method Performance ◽  
Arctic Atmosphere

Environmental contextPerfluoroalkyl compounds are of rising environmental concern because of their ubiquitous distribution in remote regions like the Arctic. The present study quantifies these contaminants in the gas and particle phases of the Canadian Arctic atmosphere. The results demonstrate the important role played by gas–particle partitioning in the transport and fate of perfluoroalkyl compounds in the atmosphere. AbstractPolyfluoroalkyl compounds (PFCs) were determined in high-volume air samples during a ship cruise onboard the Canadian Coast Guard Ship Amundsen crossing the Labrador Sea, Hudson Bay and the Beaufort Sea of the Canadian Arctic. Five PFC classes (i.e. perfluoroalkyl carboxylates (PFCAs), polyfluoroalkyl sulfonates (PFSAs), fluorotelomer alcohols (FTOHs), fluorinated sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs)) were analysed separately in the gas phase collected on PUF/XAD-2 sandwiches and in the particle phase on glass-fibre filters (GFFs). The method performance of sampling, extraction and instrumental analysis were compared between two research groups. The FTOHs were the dominant PFCs in the gas phase (20–138 pg m–3), followed by the FOSEs (0.4–23 pg m–3) and FOSAs (0.5–4.7 pg m–3). The PFCAs could only be quantified in the particle phase with low levels (<0.04–0.18 pg m–3). In the particle phase, the dominant PFC class was the FOSEs (0.3–8.6 pg m–3). The particle-associated fraction followed the general trend of: FOSEs (~25 %) > FOSAs (~9 %) > FTOHs (~1 %). Significant positive correlation between ∑FOSA concentrations in the gas phase and ambient air temperature indicate that cold Arctic surfaces, such as the sea-ice snowpack and surface seawater could be influencing FOSAs in the atmosphere.

scholarly journals Do organic surface films on sea salt aerosols influence atmospheric chemistry? – a model study

2007 ◽  
Vol 7 (21) ◽  
pp. 5555-5567 ◽  
Author(s):  
L. Smoydzin ◽  
R. von Glasow
Keyword(s):  
Mass Transfer ◽  
Liquid Phase ◽  
Gas Phase ◽  
Aqueous Phase ◽  
Atmospheric Chemistry ◽  
Organic Coating ◽  
Sea Salt ◽  
Tropospheric Chemistry ◽  
Special Focus ◽  
Sea Salt Aerosols

Abstract. Organic material from the ocean's surface can be incorporated into sea salt aerosol particles often producing a surface film on the aerosol. Such an organic coating can reduce the mass transfer between the gas phase and the aerosol phase influencing sea salt chemistry in the marine atmosphere. To investigate these effects and their importance for the marine boundary layer (MBL) we used the one-dimensional numerical model MISTRA. We considered the uncertainties regarding the magnitude of uptake reduction, the concentrations of organic compounds in sea salt aerosols and the oxidation rate of the organics to analyse the possible influence of organic surfactants on gas and liquid phase chemistry with a special focus on halogen chemistry. By assuming destruction rates for the organic coating based on laboratory measurements we get a rapid destruction of the organic monolayer within the first meters of the MBL. Larger organic initial concentrations lead to a longer lifetime of the coating but lead also to an unrealistically strong decrease of O3 concentrations as the organic film is destroyed by reaction with O3. The lifetime of the film is increased by assuming smaller reactive uptake coefficients for O3 or by assuming that a part of the organic surfactants react with OH. With regard to tropospheric chemistry we found that gas phase concentrations for chlorine and bromine species decreased due to the decreased mass transfer between gas phase and aerosol phase. Aqueous phase chlorine concentrations also decreased but aqueous phase bromine concentrations increased. Differences for gas phase concentrations are in general smaller than for liquid phase concentrations. The effect on gas phase NO2 or NO is very small (reduction less than 5%) whereas liquid phase NO2 concentrations increased in some cases by nearly 100%. We list suggestions for further laboratory studies which are needed for improved model studies.

scholarly journals Global atmospheric model for mercury including oxidation by bromine atoms

2010 ◽  
Vol 10 (24) ◽  
pp. 12037-12057 ◽  
Author(s):  
C. D. Holmes ◽  
D. J. Jacob ◽  
E. S. Corbitt ◽  
J. Mao ◽  
X. Yang ◽  
...  
Keyword(s):  
Gas Phase ◽  
Atmospheric Model ◽  
Atmospheric Mercury ◽  
The Arctic ◽  
Deposition Flux ◽  
Mercury Deposition ◽  
Photochemical Reduction ◽  
Global Atmospheric Model ◽  
Summer Maximum ◽  
Southeast Us

Abstract. Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br) as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model) and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model). We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM) concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by the Hg + Br model. Model comparisons to observed wet deposition fluxes of mercury in the US and Europe show general consistency. However the Hg + Br model does not capture the summer maximum over the southeast US because of low subtropical Br concentrations while the Hg + OH/O3 model does. Vertical profiles measured from aircraft show a decline of Hg0 above the tropopause that can be captured by both the Hg + Br and Hg + OH/O3 models, except in Arctic spring where the observed decline is much steeper than simulated by either model; we speculate that oxidation by Cl species might be responsible. The Hg + Br and Hg + OH/O3 models yield similar global budgets for the cycling of mercury between the atmosphere and surface reservoirs, but the Hg + Br model results in a much larger fraction of mercury deposited to the Southern Hemisphere oceans.

scholarly journals Air–snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS – Part 2: Mercury and its speciation

2014 ◽  
Vol 14 (8) ◽  
pp. 4135-4167 ◽  
Author(s):  
K. Toyota ◽  
A. P. Dastoor ◽  
A. Ryzhkov
Keyword(s):  
Boundary Layer ◽  
Rate Constants ◽  
Ozone Depletion ◽  
Equilibrium Constants ◽  
Ambient Air ◽  
Reaction Rates ◽  
Chemical Mechanism ◽  
The Arctic ◽  
Trace Constituents ◽  
The Impact

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.

scholarly journals Polycyclic aromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives in the Arctic boundary layer: Seasonal trends and local anthropogenic influence

2021 ◽  
Author(s):  
Tatiana Drotikova ◽  
Alena Dekhtyareva ◽  
Roland Kallenborn ◽  
Alexandre Albinet
Keyword(s):  
Boundary Layer ◽  
Ambient Air ◽  
The Arctic ◽  
Lower Latitude ◽  
Light Cycle ◽  
Photochemical Degradation ◽  
Arctic Boundary Layer ◽  
Near Surface ◽  
Sampling Campaign ◽  
Polycyclic Aromatic

Abstract. 22 PAHs, 29 oxy-PAHs, and 35 nitro-PAHs (polycyclic aromatic compounds, PACs) were measured in gaseous and particulate phases in the ambient air of Longyearbyen, the most populated settlement in Svalbard, the European Arctic. The sampling campaign started in polar night in November 2017 and lasted for 8 months until June 2018, when a light cycle reached a sunlit period with no night. The transport regimes of the near-surface, potentially polluted air masses from midlatitudes to the Arctic and the polar boundary layer meteorology were studied. The data analysis showed the observed winter PAC levels were mainly influenced by the lower latitude sources in northwestern Eurasia, while local emissions dominated in spring and summer. The highest PAC concentrations observed in spring, with PAH concentration levels a factor of 30 higher compared to the measurements at the closest background station in Svalbard (Zeppelin; in 115 km distance to Longyearbyen), were attributed to local snowmobile driving emissions. The lowest PAC concentrations were expected in summer due to enhanced photochemical degradation under the 24 h midnight sun conditions and inhibited long-range atmospheric transport. In contrast, the measured summer concentrations were notably higher than those in winter due to the harbour (ship) emissions.

Heat and Mass Transfer From Platinum-Coated Cylinders in Axisymmetric Hydrogen-Air Boundary Layers

2008 ◽  
Author(s):  
Timothy W. Tong ◽  
Mohsen M. Abou-Ellail ◽  
Yuan Li
Keyword(s):  
Boundary Layer ◽  
Mass Transfer ◽  
Gas Phase ◽  
Chemical Reactions ◽  
Reacting Flow ◽  
Surface Chemical ◽  
Surface Species ◽  
Platinum Surface ◽  
Surface Chemical Reactions ◽  
Volume Equations

Catalytic combustion of hydrogen-air mixtures involves the adsorption of the fuel and oxidant into a platinum surface, chemical reactions of the adsorbed species and the desorption of the resulting products. Re-adsorption of some produced gases is also possible. The catalytic reactions can be beneficial in porous burners that use low equivalence ratios. In this case the porous burner flame can be stabilized at low temperatures to prevent any substantial gas emissions, such as nitric oxide. The present paper is concerned with the numerical computation of heat transfer and chemical reactions in flowing hydrogen-air mixtures axisymmetrically around a platinum-coated thin cylinder. Chemical reactions are included in the gas phase and in the solid platinum surface. In the gas phase 8 species are involved in 24 elementary reactions. On the platinum hot surface, additional surface species are included that are involved in 14 additional surface chemical reactions. The platinum surface temperature is fixed, while the properties of the reacting flow are computed. The flow configuration investigated here is the parallel boundary layer reacting flow over a cylinder. Finite-volume equations are obtained by formal integration over control volumes surrounding each grid node. Up-wind differencing is used to ensure that the influence coefficients are always positive to reflect the physical effect of neighboring nodes on a typical central node. The finite-volume equations are solved iteratively for the reacting gas flow properties. On the platinum surface, surface species balance equations, under steady-state conditions, are solved numerically by an under-relaxed linear algorithm. A non-uniform computational grid is used, concentrating most of the nodes near the catalytic surface. Surface temperatures, 1150 K and 1300 K, caused fast reactions on the catalytic surface, with very slow chemical reactions in the flowing gas. These slow reactions produce mainly intermediate hydrocarbons and unstable species. The computational results for the chemical reaction boundary layer thickness and mass transfer at the gas-surface interface are correlated by non-dimensional relations, taking the Reynolds number as the independent variable. Chemical kinetic relations for the reaction rate are obtained which are dependant on reactants concentrations and surface temperature.

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