Reproducing Arctic springtime tropospheric ozone and mercury depletion events in an outdoor mesocosm sea ice facility

Abstract

Abstract. The episodic buildup of gas-phase reactive bromine species over sea ice and snowpack in the springtime Arctic plays an important role in boundary layer processes, causing annual concurrent depletion of ozone and gaseous elemental mercury (GEM) 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) are all triggered by 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 study in which we successfully reproduced ODEs and MDEs at the Sea-ice Environmental Research Facility (SERF) in Winnipeg, Canada. By monitoring ozone and GEM concentrations inside large acrylic tubes over bromide-enriched artificial seawater during sea ice freeze-and-melt cycles, we observed mid-day photochemical ozone and GEM loss in winter in the in-tube boundary layer air immediately above the sea ice surface in a pattern that is characteristic of BEE-induced ODEs and MDEs in the Arctic. The importance of UV radiation and the presence of a condensed phase (experimental sea ice or snow) in causing such reactions were demonstrated by comparing ozone and GEM concentrations between the UV-transmitting and UV-blocking acrylic tubes under different air temperatures. The ability of reproducing BEE-induced photochemical phenomena in a mesocosm in a non-polar region provides a new approach to systematically studying the cryo-photochemical processes and meteorological conditions leading to BEEs, ODEs, and MDEs in the Arctic, their role in biogeochemical cycles across the ocean–sea ice–atmosphere interface, and their sensitivities to climate change.

On the dynamics of ozone depletion events at Villum Research Station in the High Arctic

“…Cold temperatures have been shown to be an important factor influencing ODEs (Simpson et al, 2007b(Simpson et al, , 2015, indeed frozen heterogeneous surfaces can lead to the release of bromine, which is known from studies using reanalysis products (Seo et al, 2020;Zilker et al, 2023), laboratory experiments (Abbatt et al, 2012;Halfacre et al, 2019), and mesocosm/field studies (Gao et al, 2022;Pöhler et al, 2010;Pratt et al, 2013;Swanson et al, 2020). Observational evidence has shown halogen activation ceases at abovefreezing temperatures (Burd et al, 2017;Jeong et al, 2022).…”

Experimental Determination of Mercury Photoreduction Rates in Cloudwater

“…The instrument reports Hg 0 concentrations at a 5-min resolution. A detailed description of the method can be found in Gao et al (2022). During the experiment, the instrument was routinely calibrated with an internal Hg permeation source and the relative standard deviation was 2.8% (n = 12).…”

Application of Satellite‐Based Detections of Arctic Bromine Explosion Events Within GEOS‐Chem

“…These bromine explosions drive boundary layer ozone depletion events (ODEs), where ozone (O 3 ) rapidly decreases from background mixing ratios to levels near zero (e.g., Bottenheim & Chan, 2006; Halfacre et al., 2014; Jones et al., 2006; Wessel et al., 1998). During ODEs, halogens become the main tropospheric oxidant, impacting the lifetimes of Arctic pollutants (Bloss et al., 2010; Evans et al., 2003) and increasing the deposition and biological uptake of oxidized mercury (Gao et al., 2022; Holmes et al., 2006; Schroeder et al., 1998; Stephens et al., 2012; S. Wang et al., 2019a). The underlying process resulting in bromine explosion events is connected to sea ice and thus is susceptible to the influence of climate change in polar regions (Pratt, 2019).…”