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Deep convection in the Asian summer monsoon is a significant transport process for lifting pollutants from the planetary boundary layer to the tropopause level. This process enables efficient injection into the stratosphere of reactive species such as chlorinated very short-lived substances (Cl-VSLSs) that deplete ozone. Past studies of convective transport associated with the Asian summer monsoon have focused mostly on the south Asian summer monsoon. Airborne observations reported in this work identify the East Asian summer monsoon convection as an effective transport pathway that carried record-breaking levels of ozone-depleting Cl-VSLSs (mean organic chlorine from these VSLSs ~500 ppt) to the base of the stratosphere. These unique observations show total organic chlorine from VSLSs in the lower stratosphere over the Asian monsoon tropopause to be more than twice that previously reported over the tropical tropopause. Considering the recently observed increase in Cl-VSLS emissions and the ongoing strengthening of the East Asian summer monsoon under global warming, our results highlight that a reevaluation of the contribution of Cl-VSLS injection via the Asian monsoon to the total stratospheric chlorine budget is warranted.

 

Abstract 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 (HClO 3 ) and perchloric (HClO 4 ) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO 3 and HClO 4 . Significant levels of HClO 3 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 × 10 6 molecule cm −3 . The increase in HClO 3 , concomitantly with that in HClO 4 , was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO 3 and HClO 4 by hydroxyl radicals. HClO 3 and HClO 4 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. 

The catalytic depletion of Antarctic stratospheric ozone is linked to anthropogenic emissions of chlorine and bromine. Despite its larger ozone-depleting efficiency, the contribution of ocean-emitted iodine to ozone hole chemistry has not been evaluated, due to the negligible iodine levels previously reported to reach the stratosphere. Based on the recently observed range (0.77 ± 0.1 parts per trillion by volume [pptv]) of stratospheric iodine injection, we use the Whole Atmosphere Community Climate Model to assess the role of iodine in the formation and recent past evolution of the Antarctic ozone hole. Our 1980–2015 simulations indicate that iodine can significantly impact the lower part of the Antarctic ozone hole, contributing, on average, 10% of the lower stratospheric ozone loss during spring (up to 4.2% of the total stratospheric column). We find that the inclusion of iodine advances the beginning and delays the closure stages of the ozone hole by 3 d to 5 d, increasing its area and mass deficit by 11% and 20%, respectively. Despite being present in much smaller amounts, and due to faster gas-phase photochemical reactivation, iodine can dominate (∼73%) the halogen-mediated lower stratospheric ozone loss during summer and early fall, when the heterogeneous reactivation of inorganic chlorine and bromine reservoirs is reduced. The stratospheric ozone destruction caused by 0.77 pptv of iodine over Antarctica is equivalent to that of 3.1 (4.6) pptv of biogenic very short-lived bromocarbons during spring (rest of sunlit period). The relative contribution of iodine to future stratospheric ozone loss is likely to increase as anthropogenic chlorine and bromine emissions decline following the Montreal Protocol. 

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. 

Abstract. Bromine released from the decomposition of short-lived brominated source gases contributes as a sink of ozone in the lower stratosphere.The two major contributors are CH2Br2 and CHBr3.In this study, we investigate the global seasonal distribution of these two substances, based on four High Altitude and Long Range Research Aircraft (HALO) missions, the HIAPER Pole-to-Pole Observations (HIPPO) mission, and the Atmospheric Tomography (ATom) mission.Observations of CH2Br2 in the free and upper troposphere indicate a pronounced seasonality in both hemispheres, with slightly larger mixing ratios in the Northern Hemisphere (NH).Compared to CH2Br2, CHBr3 in these regions shows larger variability and less clear seasonality, presenting larger mixing ratios in winter and autumn in NH midlatitudes to high latitudes.The lowermost stratosphere of SH and NH shows a very similar distribution of CH2Br2 in hemispheric spring with differences well below 0.1 ppt, while the differences in hemispheric autumn are much larger with substantially smaller values in the SH than in the NH.This suggests that transport processes may be different in both hemispheric autumn seasons, which implies that the influx of tropospheric air (“flushing”) into the NH lowermost stratosphere is more efficient than in the SH.The observations of CHBr3 support the suggestion, with a steeper vertical gradient in the upper troposphere and lower stratosphere in SH autumn than in NH autumn.However, the SH database is insufficient to quantify this difference.We further compare the observations to model estimates of TOMCAT (Toulouse Off-line Model of Chemistry And Transport) and CAM-Chem (Community Atmosphere Model with Chemistry, version 4), both using the same emission inventory of Ordóñez et al. (2012).The pronounced tropospheric seasonality of CH2Br2 in the SH is not reproduced by the models,presumably due to erroneous seasonal emissions or atmospheric photochemical decomposition efficiencies.In contrast, model simulations of CHBr3 show a pronounced seasonality in both hemispheres, which is not confirmed by observations.The distributions of both species in the lowermost stratosphere of the Northern and Southern hemispheres are overall well captured by the models with the exception of southern hemispheric autumn,where both models present a bias that maximizes in the lowest 40 K above the tropopause, with considerably lower mixing ratios in the observations.Thus, both models reproduce equivalent flushing in both hemispheres, which is not confirmed by the limited available observations.Our study emphasizes the need for more extensive observations in the SH to fully understand the impact of CH2Br2 and CHBr3 on lowermost-stratospheric ozone loss and to help constrain emissions.

 

Iodine is an atmospheric trace element emitted from oceans that efficiently destroys ozone (O 3 ). Low O 3 in airborne dust layers is frequently observed but poorly understood. We show that dust is a source of gas-phase iodine, indicated by aircraft observations of iodine monoxide (IO) radicals inside lofted dust layers from the Atacama and Sechura Deserts that are up to a factor of 10 enhanced over background. Gas-phase iodine photochemistry, commensurate with observed IO, is needed to explain the low O 3 inside these dust layers (below 15 ppbv; up to 75% depleted). The added dust iodine can explain decreases in O 3 of 8% regionally and affects surface air quality. Our data suggest that iodate reduction to form volatile iodine species is a missing process in the geochemical iodine cycle and presents an unrecognized aeolian source of iodine. Atmospheric iodine has tripled since 1950 and affects ozone layer recovery and particle formation. 

Abstract Unlike bromine, the effect of iodine chemistry on the Arctic surface ozone budget is poorly constrained. We present ship-based measurements of halogen oxides in the high Arctic boundary layer from the sunlit period of March to October 2020 and show that iodine enhances springtime tropospheric ozone depletion. We find that chemical reactions between iodine and ozone are the second highest contributor to ozone loss over the study period, after ozone photolysis-initiated loss and ahead of bromine. 

Chemistry Climate Models (CCMs) are essential tools for characterizing and predicting the role of atmospheric composition and chemistry in Earth's climate system. This study demonstrates the use of airborne in situ observations to diagnose the representation of chemical composition and transport by CCMs. Process‐based diagnostics using dynamical and chemical coordinates are presented which minimize the spatial and temporal sampling differences between airborne in situ measurements and CCM grid points. The chosen process is the chemical impact of the Asian summer monsoon (ASM), where deep convection serves as a rapid transport pathway for surface emissions to reach the upper troposphere and lower stratosphere (UTLS). We examine two CCM configurations for their representation of the ASM UTLS using a set of airborne observations from south Asia. The diagnostics reveal good model performance at representing tropospheric tracer distribution throughout the troposphere and lower stratosphere, and excellent representation of chemical aging in the lower stratosphere when chemical loss is dominated by photolysis. Identified model limitations include the use of zonally averaged mole fraction boundary conditions for species with sufficiently short tropospheric lifetimes, which may obscure enhanced regional emissions sources. Overall, the diagnostics underscore the skill of current‐generation models at representing pollution transport from the boundary layer to the stratosphere via the ASM mechanism, and demonstrate the strength of airborne in situ observations toward characterizing this representation.

 

Abstract. In this paper, we present a new version of the chemistry–climate model SOCOL-AERv2 supplemented by an iodine chemistry module. We perform three 20-year ensemble experiments to assess the validity of the modeled iodine and to quantify the effects of iodine on ozone. The iodine distributions obtained with SOCOL-AERv2-I agree well with AMAX-DOAS observations and with CAM-chem model simulations. For the present-day atmosphere, the model suggests that the iodine-induced chemistry leads to a 3 %–4 % reduction in the ozone column, which is greatest at high latitudes. The model indicates the strongest influence of iodine in the lower stratosphere with 30 ppbv less ozone at low latitudes and up to 100 ppbv less at high latitudes. In the troposphere, the account of the iodine chemistry reduces the tropospheric ozone concentration by 5 %–10 % depending on geographical location. In the lower troposphere, 75 % of the modeled ozone reduction originates from inorganic sources of iodine, 25 % from organic sources of iodine. At 50 hPa, the results show that the impacts of iodine from both sources are comparable. Finally, we determine the sensitivity of ozone to iodine by applying a 2-fold increase in iodine emissions, as it might be representative for iodine by the end of this century. This reduces the ozone column globally by an additional 1.5 %–2.5 %. Our results demonstrate the sensitivity of atmospheric ozone to iodine chemistry for present and future conditions, but uncertainties remain high due to the paucity of observational data of iodine species.