skip to main content


The NSF Public Access Repository (NSF-PAR) system and access will be unavailable from 11:00 PM ET on Thursday, June 13 until 2:00 AM ET on Friday, June 14 due to maintenance. We apologize for the inconvenience.

Title: The Role of Snow in Controlling Halogen Chemistry and Boundary Layer Oxidation During Arctic Spring: A 1D Modeling Case Study

Reactive chlorine and bromine species emitted from snow and aerosols can significantly alter the oxidative capacity of the polar boundary layer. However, halogen production mechanisms from snow remain highly uncertain, making it difficult for most models to include descriptions of halogen snow emissions and to understand the impact on atmospheric chemistry. We investigate the influence of Arctic halogen emissions from snow on boundary layer oxidation processes using a one‐dimensional atmospheric chemistry and transport model (PACT‐1D). To understand the combined impact of snow emissions and boundary layer dynamics on atmospheric chemistry, we model Cl2and Br2primary emissions from snow and include heterogeneous recycling of halogens on both snow and aerosols. We focus on a 2‐day case study from the 2009 Ocean‐Atmosphere‐Sea Ice‐Snowpack campaign at Utqiaġvik, Alaska. The model reproduces both the diurnal cycle and high quantity of Cl2observed, along with the measured concentrations of Br2, BrO, and HOBr. Due to the combined effects of emissions, recycling, vertical mixing, and atmospheric chemistry, reactive chlorine is typically confined to the lowest 15 m of the atmosphere, while bromine can impact chemistry up to and above the surface inversion height. Upon including halogen emissions and recycling, the concentration of HOx(HOx = OH + HO2) at the surface increases by as much as a factor of 30 at mid‐day. The change in HOxdue to halogen chemistry, as well as chlorine atoms derived from snow emissions, significantly reduce volatile organic compound lifetimes within a shallow layer near the surface.

more » « less
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
DOI PREFIX: 10.1029
Date Published:
Journal Name:
Journal of Geophysical Research: Atmospheres
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Marine cloud brightening (MCB) is proposed to offset global warming by emitting sea salt aerosols to the tropical marine boundary layer, which increases aerosol and cloud albedo. Sea salt aerosol is the main source of tropospheric reactive chlorine (Cly) and bromine (Bry). The effects of additional sea salt on atmospheric chemistry have not been explored. We simulate sea salt aerosol injections for MCB under two scenarios (212–569 Tg/a) in the GEOS‐Chem global chemical transport model, only considering their impacts as a halogen source. Globally, tropospheric Clyand Bryincrease (20–40%), leading to decreased ozone (−3 to −6%). Consequently, OH decreases (−3 to −5%), which increases the methane lifetime (3–6%). Our results suggest that the chemistry of the additional sea salt leads to minor total radiative forcing compared to that of the sea salt aerosol itself (~2%) but may have potential implications for surface ozone pollution in tropical coastal regions.

    more » « less
  2. Near-surface mercury and ozone depletion events occur in the lowest part of the atmosphere during Arctic spring. Mercury depletion is the first step in a process that transforms long-lived elemental mercury to more reactive forms within the Arctic that are deposited to the cryosphere, ocean, and other surfaces, which can ultimately get integrated into the Arctic food web. Depletion of both mercury and ozone occur due to the presence of reactive halogen radicals that are released from snow, ice, and aerosols. In this work, we added a detailed description of the Arctic atmospheric mercury cycle to our recently published version of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem 4.3.3) that includes Arctic bromine and chlorine chemistry and activation/recycling on snow and aerosols. The major advantage of our modelling approach is the online calculation of bromine concentrations and emission/recycling that is required to simulate the hourly and daily variability of Arctic mercury depletion. We used this model to study coupling between reactive cycling of mercury, ozone, and bromine during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) spring season in 2020 and evaluated results compared to land-based, ship-based, and remote sensing observations. The model predicts that elemental mercury oxidation is driven largely by bromine chemistry and that particulate mercury is the major form of oxidized mercury. The model predicts that the majority (74%) of oxidized mercury deposited to land-based snow is re-emitted to the atmosphere as gaseous elemental mercury, while a minor fraction (4%) of oxidized mercury that is deposited to sea ice is re-emitted during spring. Our work demonstrates that hourly differences in bromine/ozone chemistry in the atmosphere must be considered to capture the springtime Arctic mercury cycle, including its integration into the cryosphere and ocean. 
    more » « less
  3. Abstract. We use the GEOS-Chem chemical transport model to examine theinfluence of bromine release from blowing-snow sea salt aerosol (SSA) onspringtime bromine activation and O3 depletion events (ODEs) in theArctic lower troposphere. We evaluate our simulation against observations oftropospheric BrO vertical column densities (VCDtropo) from the GOME-2 (second Global Ozone Monitoring Experiment)and Ozone Monitoring Instrument (OMI) spaceborne instruments for 3 years (2007–2009), as well asagainst surface observations of O3. We conduct a simulation withblowing-snow SSA emissions from first-year sea ice (FYI; with a surface snowsalinity of 0.1 psu) and multi-year sea ice (MYI; with a surface snowsalinity of 0.05 psu), assuming a factor of 5 bromide enrichment of surfacesnow relative to seawater. This simulation captures the magnitude ofobserved March–April GOME-2 and OMI VCDtropo to within 17 %, as wellas their spatiotemporal variability (r=0.76–0.85). Many of the large-scalebromine explosions are successfully reproduced, with the exception of eventsin May, which are absent or systematically underpredicted in the model. Ifwe assume a lower salinity on MYI (0.01 psu), some of the bromine explosionsevents observed over MYI are not captured, suggesting that blowing snow overMYI is an important source of bromine activation. We find that the modeledatmospheric deposition onto snow-covered sea ice becomes highly enriched inbromide, increasing from enrichment factors of ∼5 inSeptember–February to 10–60 in May, consistent with composition observations of freshly fallen snow. We propose that this progressive enrichment indeposition could enable blowing-snow-induced halogen activation to propagateinto May and might explain our late-spring underestimate in VCDtropo.We estimate that the atmospheric deposition of SSA could increase snow salinityby up to 0.04 psu between February and April, which could be an importantsource of salinity for surface snow on MYI as well as FYI covered by deepsnowpack. Inclusion of halogen release from blowing-snow SSA in oursimulations decreases monthly mean Arctic surface O3 by 4–8 ppbv(15 %–30 %) in March and 8–14 ppbv (30 %–40 %) in April. We reproduce atransport event of depleted O3 Arctic air down to 40∘ Nobserved at many sub-Arctic surface sites in early April 2007. While oursimulation captures 25 %–40 % of the ODEs observed at coastal Arctic surfacesites, it underestimates the magnitude of many of these events and entirelymisses 60 %–75 % of ODEs. This difficulty in reproducing observed surfaceODEs could be related to the coarse horizontal resolution of the model, theknown biases in simulating Arctic boundary layer exchange processes, thelack of detailed chlorine chemistry, and/or the fact that we did not includedirect halogen activation by snowpack chemistry. 
    more » « less
  4. Abstract. We present an updated mechanism for tropospheric halogen (Cl + Br + I) chemistry in the GEOS-Chem global atmospheric chemical transportmodel and apply it to investigate halogen radical cycling and implications for tropospheric oxidants. Improved representation of HOBr heterogeneouschemistry and its pH dependence in our simulation leads to less efficient recycling and mobilization of bromine radicals and enables the model toinclude mechanistic sea salt aerosol debromination without generating excessive BrO. The resulting global mean tropospheric BrO mixingratio is 0.19 ppt (parts per trillion), lower than previous versions of GEOS-Chem. Model BrO shows variable consistency and biases in comparison tosurface and aircraft observations in marine air, which are often near or below the detection limit. The model underestimates the daytimemeasurements of Cl2 and BrCl from the ATom aircraft campaign over the Pacific and Atlantic, which if correct would imply a very largemissing primary source of chlorine radicals. Model IO is highest in the marine boundary layer and uniform in the free troposphere, with a globalmean tropospheric mixing ratio of 0.08 ppt, and shows consistency with surface and aircraft observations. The modeled global meantropospheric concentration of Cl atoms is 630 cm−3, contributing 0.8 % of the global oxidation of methane, 14 % of ethane,8 % of propane, and 7 % of higher alkanes. Halogen chemistry decreases the global tropospheric burden of ozone by 11 %,NOx by 6 %, and OH by 4 %. Most of the ozone decrease is driven by iodine-catalyzed loss. The resulting GEOS-Chem ozonesimulation is unbiased in the Southern Hemisphere but too low in the Northern Hemisphere. 
    more » « less
  5. Abstract. Mercury (Hg) is emitted to the atmosphere mainly as volatile elemental Hg0. Oxidation to water-soluble HgII plays a major role in Hg deposition to ecosystems. Here, we implement a new mechanism for atmospheric Hg0HgII redox chemistry in the GEOS-Chem global model and examine the implications for the global atmospheric Hg budget and deposition patterns. Our simulation includes a new coupling of GEOS-Chem to an ocean general circulation model (MITgcm), enabling a global 3-D representation of atmosphere–ocean Hg0HgII cycling. We find that atomic bromine (Br) of marine organobromine origin is the main atmospheric Hg0 oxidant and that second-stage HgBr oxidation is mainly by the NO2 and HO2 radicals. The resulting chemical lifetime of tropospheric Hg0 against oxidation is 2.7 months, shorter than in previous models. Fast HgII atmospheric reduction must occur in order to match the  ∼ 6-month lifetime of Hg against deposition implied by the observed atmospheric variability of total gaseous mercury (TGM ≡ Hg0+HgII(g)). We implement this reduction in GEOS-Chem as photolysis of aqueous-phase HgII–organic complexes in aerosols and clouds, resulting in a TGM lifetime of 5.2 months against deposition and matching both mean observed TGM and its variability. Model sensitivity analysis shows that the interhemispheric gradient of TGM, previously used to infer a longer Hg lifetime against deposition, is misleading because Southern Hemisphere Hg mainly originates from oceanic emissions rather than transport from the Northern Hemisphere. The model reproduces the observed seasonal TGM variation at northern midlatitudes (maximum in February, minimum in September) driven by chemistry and oceanic evasion, but it does not reproduce the lack of seasonality observed at southern hemispheric marine sites. Aircraft observations in the lowermost stratosphere show a strong TGM–ozone relationship indicative of fast Hg0 oxidation, but we show that this relationship provides only a weak test of Hg chemistry because it is also influenced by mixing. The model reproduces observed Hg wet deposition fluxes over North America, Europe, and China with little bias (0–30%). It reproduces qualitatively the observed maximum in US deposition around the Gulf of Mexico, reflecting a combination of deep convection and availability of NO2 and HO2 radicals for second-stage HgBr oxidation. However, the magnitude of this maximum is underestimated. The relatively low observed Hg wet deposition over rural China is attributed to fast HgII reduction in the presence of high organic aerosol concentrations. We find that 80% of HgII deposition is to the global oceans, reflecting the marine origin of Br and low concentrations of organic aerosols for HgII reduction. Most of that deposition takes place to the tropical oceans due to the availability of HO2 and NO2 for second-stage HgBr oxidation.

    more » « less