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1. Sensitivity of Iodine-Mediated Stratospheric Ozone Loss Chemistry to Future Chemistry-Climate Scenarios

   https://doi.org/10.3389/feart.2021.617586  

   Klobas, J. Eric; Hansen, Janina; Weisenstein, Debra K.; Kennedy, Robert P.; Wilmouth, David M. (May 2021, Frontiers in Earth Science)

   null (Ed.)

   As the chemical and physical state of the stratosphere evolves, so too will the rates of important ozone-destroying reactions. In this work, we evaluate the chemistry-climate sensitivity of reactions of stratospheric iodine, reporting the iodine alpha factor (the efficiency of ozone loss mediated by a single iodine atom relative to the ozone loss mediated by a single chlorine atom) and the iodine eta factor (the efficiency of ozone loss mediated by a single iodine atom relative to the ozone loss mediated by a single chlorine atom in a benchmark chemistry-climate state) as a function of future greenhouse gas emissions scenario. We find that iodine-mediated ozone loss is much less sensitive to future changes in the state of the stratosphere than chlorine- and bromine-mediated reactions. Additionally, we demonstrate that the inclusion of the heterogeneous reaction of ozone with aqueous iodide in stratospheric aerosol produces substantial enhancements in the iodine alpha and eta factors relative to evaluations that consider gas-phase iodine reactions only. We conclude that the share of halogen-induced ozone loss due to reactions of iodine will likely be greater in the future stratosphere than it is today. 

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2. Reformulating the bromine alpha factor and equivalent effective stratospheric chlorine (EESC): evolution of ozone destruction rates of bromine and chlorine in future climate scenarios

   https://doi.org/10.5194/acp-20-9459-2020  

   Klobas, J. Eric; Weisenstein, Debra K.; Salawitch, Ross J.; Wilmouth, David M. (January 2020, Atmospheric Chemistry and Physics)

   null (Ed.)

   Abstract. Future trajectories of the stratospheric trace gas background will alter the rates of bromine- and chlorine-mediated catalytic ozone destruction via changes in the partitioning of inorganic halogen reservoirs and the underlying temperature structure of the stratosphere. The current formulation of the bromine alpha factor, the ozone-destroying power of stratospheric bromine atoms relative to stratospheric chlorine atoms, is invariant with the climate state. Here, we refactor the bromine alpha factor, introducing normalization to a benchmark chemistry–climate state, and formulate Equivalent Effective Stratospheric Benchmark-normalized Chlorine (EESBnC) to reflect changes in the rates of both bromine- and chlorine-mediated ozone loss catalysis with time. We show that the ozone-processing power of the extrapolar stratosphere is significantly perturbed by future climate assumptions. Furthermore, we show that our EESBnC-based estimate of the extrapolar ozone recovery date is in closer agreement with extrapolar ozone recovery dates predicted using more sophisticated 3-D chemistry–climate models than predictions made using equivalent effective stratospheric chlorine (EESC). 

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3. On Recent Large Antarctic Ozone Holes and Ozone Recovery Metrics

   https://doi.org/10.1029/2021GL095232  

   Stone, K. A.; Solomon, S.; Kinnison, D. E.; Mills, Michael J. (November 2021, Geophysical Research Letters)

   Abstract The 2015 and 2020 ozone holes set record sizes in October–December. We show that these years, as well as other recent large ozone holes, still adhere to a fundamental recovery metric: the later onset of early spring ozone depletion as chlorine and bromine diminishes. This behavior is also captured in the Whole Atmosphere Chemistry Climate Model. We quantify observed recovery trends of the onset of the ozone hole and in the size of the September ozone hole, with good model agreement. A substantial reduction in ozone hole depth during September over the past decade is also seen. Our results indicate that, due to dynamical phenomena, it is likely that large ozone holes will continue to occur intermittently in October–December, but ozone recovery will still be detectable through the later onset, smaller, and less deep September ozone holes: metrics that are governed more by chemical processes. 

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4. Implications of Snowpack Reactive Bromine Production for Arctic Ice Core Bromine Preservation

   https://doi.org/10.1029/2023JD039257  

   Zhai, Shuting; Swanson, William; McConnell, Joseph R.; Chellman, Nathan; Opel, Thomas; Sigl, Michael; Meyer, Hanno; Wang, Xuan; Jaeglé, Lyatt; Stutz, Jochen; et al (October 2023, Journal of Geophysical Research: Atmospheres)

   Abstract Snowpack emissions are recognized as an important source of gas‐phase reactive bromine in the Arctic and are necessary to explain ozone depletion events in spring caused by the catalytic destruction of ozone by halogen radicals. Quantifying bromine emissions from snowpack is essential for interpretation of ice‐core bromine. We present ice‐core bromine records since the pre‐industrial (1750 CE) from six Arctic locations and examine potential post‐depositional loss of snowpack bromine using a global chemical transport model. Trend analysis of the ice‐core records shows that only the high‐latitude coastal Akademii Nauk (AN) ice core from the Russian Arctic preserves significant trends since pre‐industrial times that are consistent with trends in sea ice extent and anthropogenic emissions from source regions. Model simulations suggest that recycling of reactive bromine on the snow skin layer (top 1 mm) results in 9–17% loss of deposited bromine across all six ice‐core locations. Reactive bromine production from below the snow skin layer and within the snow photic zone is potentially more important, but the magnitude of this source is uncertain. Model simulations suggest that the AN core is most likely to preserve an atmospheric signal compared to five Greenland ice cores due to its high latitude location combined with a relatively high snow accumulation rate. Understanding the sources and amount of photochemically reactive snow bromide in the snow photic zone throughout the sunlit period in the high Arctic is essential for interpreting ice‐core bromine, and warrants further lab studies and field observations at inland locations. 

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5. Arctic tropospheric ozone seasonality, depletion, and oil field influence

   https://doi.org/10.1039/D4FD00166D  

   Widmaier, Evelyn M; Jensen, Andrew R; Pratt, Kerri A (November 2024, Faraday Discussions)

   Near-surface tropospheric ozone depletion events (ODEs) occur in the polar regions during springtime when ozone reacts with bromine radicals, driving tropospheric ozone mole ratios below 15 ppb (part-per-billion; nmol mol−1). ODEs alter atmospheric oxidative capacity by influencing halogen radical recycling mechanisms and the photochemical production of hydroxyl radicals (˙OH). Herein, we examined five years of continuous ozone measurements at two coastal Arctic sites: Utqiaġvik, Alaska and ∼260 km southeast at Oliktok Point, within the North Slope of Alaska oil fields. These data informed seasonal ozone trends, springtime ozone depletion, and the influence of oil field combustion emissions. Ozone depletion occurred frequently during spring: 35% of the time at Utqiaġvik and 40% at Oliktok Point. ODEs often occurred concurrently at both sites (40–92% of observed ODEs per year), supporting spatially widespread ozone depletion. Observed ozone depletion timescales are consistent with transport of ozone-depleted air masses, suggesting regional active bromine chemistry. Local-scale ozone depletion affecting individual sites occurred less frequently. Ozone depletion typically coincided with calm winds and had no clear dependence on temperature. Consistently lower ozone mole ratios year-round at Oliktok Point, compared to Utqiaġvik, indicate local-scale ozone titration within the stable boundary layer by nitric oxide (NO˙) combustion emissions in the Arctic oil fields. Oxidation of combustion-derived volatile organic compounds in the presence of NOx also likely contributes to ozone formation downwind, for example at Utqiaġvik, pointing to complex local and regional impacts of combustion emissions as Arctic anthropogenic activity increases. 

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