Substantial contribution of iodine to Arctic ozone destruction

Benavent, Nuria; Mahajan, Anoop S.; Li, Qinyi; Cuevas, Carlos A.; Schmale, Julia; Angot, Hélène; Jokinen, Tuija; Quéléver, Lauriane L. J.; Blechschmidt, Anne-Marlene; Zilker, Bianca; Richter, Andreas; Serna, J.Adl.O.; García-Nieto, David; Fernández, Rafael P.; Skov, Henrik; Dumitrascu, Adela; Pereira, Patric Simões; Abrahamsson, Katarina; Bucci, Silvia; Dütsch, Marina; Stohl, Andreas; Beck, Ivo; Laurila, Tiia; Blomquist, Byron; Howard, Dean; Archer, Stephen D.; Bariteau, Ludovic; Helmig, Detlev; Hueber, Jacques; Jacobi, Hans-Werner; Posman, Kevin; Dada, Lubna; Daellenbach, Kaspar R.; Saiz‐Lopez, Alfonso

doi:10.1038/s41561-022-01018-w

Cited by 28 publications

(13 citation statements)

References 40 publications

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“…In addition to photolysis, the produced ClO can then react with BrO/ClO to produce OClO, or undergo loss through reactions with OH, HO 2 , NO and NO 2 , CH 3 OO, and CH 3 COOO 2 . Abundant BrO and ClO must have been present during the encountered ozone-depletion events, as have been previously demonstrated by many studies 2,3,[31][32][33][34][35][36][37] , and significant levels of BrO have been observed in spring during the MOSAiC campaign 38 . By using the previously reported typical ranges of BrO, ClO, and HO 2 levels during Arctic ozone-depletion events 11,[32][33][34][35][36][37][38][39][40] , we estimate that the reaction rate of ClO + BrO is much higher than that of the ClO + ClO and ClO + HO 2 channels (section S1 in the Supplementary Information, SI), suggesting that the increase in BrO during ozone depletion events drives the OClO formation.…”

Section: Potential Formation Mechanism Of Atmospheric Chlorine Oxyacidssupporting

confidence: 63%

“…Abundant BrO and ClO must have been present during the encountered ozone-depletion events, as have been previously demonstrated by many studies 2,3,[31][32][33][34][35][36][37] , and significant levels of BrO have been observed in spring during the MOSAiC campaign 38 . By using the previously reported typical ranges of BrO, ClO, and HO 2 levels during Arctic ozone-depletion events 11,[32][33][34][35][36][37][38][39][40] , we estimate that the reaction rate of ClO + BrO is much higher than that of the ClO + ClO and ClO + HO 2 channels (section S1 in the Supplementary Information, SI), suggesting that the increase in BrO during ozone depletion events drives the OClO formation. The reaction of ClO + OH, ClO + CH 3 OO, and ClO + CH 3 COOO are insignificant; however, the presence of typical levels of NO x (NO and NO 2 ) in the Arctic (i.e., 1−40 ppt) can compete with BrO for ClO (section S1 in SI).…”

Section: Potential Formation Mechanism Of Atmospheric Chlorine Oxyacidssupporting

confidence: 63%

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Widespread detection of chlorine oxyacids in the Arctic atmosphere

et al. 2023

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Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO3) and perchloric (HClO4) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO3 and HClO4. Significant levels of HClO3 were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 106 molecule cm−3. The increase in HClO3, concomitantly with that in HClO4, was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO3 and HClO4 by hydroxyl radicals. HClO3 and HClO4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.

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Section: Potential Formation Mechanism Of Atmospheric Chlorine Oxyacidssupporting

confidence: 63%

Section: Potential Formation Mechanism Of Atmospheric Chlorine Oxyacidssupporting

confidence: 63%

Widespread detection of chlorine oxyacids in the Arctic atmosphere

et al. 2023

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“…In polar regions, Br y is largely responsible for surface ozone depletion events (ODEs) in coastal regions in the spring (Barrie et al., 1988; Oltmans et al., 1989, 2012). Reactive iodine also plays a role in ODEs (Benavent et al., 2022), with a smaller contribution from reactive chlorine (Wang et al., 2021). Br y is also associated with atmospheric mercury depletion events in the Arctic (Horowitz et al., 2017; Steffen et al., 2008).…”

Section: Introductionmentioning

confidence: 99%

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

Zhai,

Swanson,

McConnell

et al. 2023

JGR Atmospheres

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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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“…Changes in O 3 concentrations at this time of year may be driven by changes in ODE frequency linked to climate change or weather patterns (Oltmans et al, 2012). ODEs lead to zero or very low springtime O 3 due to bromine released from frost flowers or blowing snow (on sea-ice) (Simpson et al, 2007;Yang et al, 2008Yang et al, , 2010 or iodine compounds with a possible oceanic source (Benavent et al, 2022). Increasing prevalence of first year sea-ice leading to increasing sea-spray aero sols from blowing snow (Confer et al, 2023) may explain increases in springtime tropospheric bromine oxide, observed from satellites, along the north coast of Greenland and central Arctic Ocean (Bougoudis et al, 2020).…”

Section: Discussionmentioning

confidence: 99%

Arctic Tropospheric Ozone Trends

Law,

Hjorth,

Pernov

et al. 2023

Geophysical Research Letters

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Observed trends in tropospheric ozone, an important air pollutant and short‐lived climate forcer (SLCF), are estimated using available surface and ozonesonde profile data for 1993–2019, using a coherent methodology, and compared to modeled trends (1995–2015) from the Arctic Monitoring Assessment Program SLCF 2021 assessment. Increases in observed surface ozone at Arctic coastal sites, notably during winter, and concurrent decreasing trends in surface carbon monoxide, are generally captured by multi‐model median trends. Wintertime increases are also estimated in the free troposphere at most Arctic sites, with decreases during spring months. Winter trends tend to be overestimated by the multi‐model medians. Springtime surface ozone increases in northern coastal Alaska are not simulated while negative springtime trends in northern Scandinavia are not always reproduced. Possible reasons for observed changes and model performance are discussed including decreasing precursor emissions, changing ozone dry deposition, and variability in large‐scale meteorology.

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Substantial contribution of iodine to Arctic ozone destruction

Cited by 28 publications

References 40 publications

Widespread detection of chlorine oxyacids in the Arctic atmosphere

Widespread detection of chlorine oxyacids in the Arctic atmosphere

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

Arctic Tropospheric Ozone Trends

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