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Oceanic dimethyl sulfide (DMS) is the largest natural source of atmospheric sulfur. DMS is biologically produced in seawater and emitted into the atmosphere, where its oxidation products contribute to aerosol formation with consequences for cloud albedo and the Earth’s radiative budget and climate. Climate model projections of how DMS emissions change with global warming are largely uncertain, even contradictory. Here, we use machine-learning models trained with biome-resolved global observations to simulate seawater DMS concentrations (1850 to 2100) using physico-chemical and biological predictors from eight CMIP6 models. The scatter in current projections is largely reduced, and globally averaged seawater DMS concentrations are predicted to decrease in the coming decades. However, global DMS emissions will increase due to rising surface wind speeds and sea surface temperatures which contradicts the current AR6 assessment that the DMS flux will reduce in the future. Concurrence of increasing DMS emissions and declining anthropogenic sulfur dioxide emissions suggests an increase in the relative importance of DMS to sulfate aerosol formation and its climate cooling impact. 

Abstract. Tropospheric reactive iodine influences the oxidizing capacity of the atmosphere and serves as an important source of ultra-fine particles. However, the paucity of observations of gas-phase and aerosol iodine, combined with incomplete understanding and representation of iodine chemistry in models, leads to substantial uncertainties in understanding iodine abundance, speciation, and impacts. Motivated by known gaps in previous modeling studies, we introduced speciated aerosol iodine and aerosol iodide recycling to the global chemical transport model, GEOS-Chem. Modeled aerosol iodine is speciated into fine and coarse mode soluble organic iodine (SOI), iodate, and iodide. Aerosol iodide is recycled into the gas phase via heterogeneous chemistry involving halogen nitrates and hypohalous acids to form I2, ICl, and IBr, which represents an additional source of gas-phase iodine to the atmosphere. Iodide dehalogenation doubles the tropospheric burden of reactive iodine (Iy) while reducing model-measurement bias for IO and aerosol iodine. The rate of aerosol iodine conversion to Iy is more than twice as fast as the combined rates of inorganic ocean emissions and the photolysis of organic iodine gases, suggesting that aerosols are important in mediating the abundance and lifetime of tropospheric Iy. The incorporation of SOI and iodate into the model prevents iodide dehalogenation by partitioning iodide into less reactive reservoirs, which has a stabilizing effect for reactive iodine chemistry. These findings have implications for reactive halogen abundances and global oxidant budgets in the troposphere. 

Abstract 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 Chlorinated very short‐lived substances (Cl‐VSLS) are ubiquitous in the troposphere and can contribute to the stratospheric chlorine budget. In this study, we present measurements of atmospheric dichloromethane (CH₂Cl₂), tetrachloroethene (C₂Cl₄), chloroform (CHCl₃), and 1,2‐dichloroethane (1,2‐DCA) obtained during the National Aeronautics and Space Administration (NASA) Atmospheric Tomography (ATom) global‐scale aircraft mission (2016–2018), and use the Community Earth System Model (CESM) updated with recent chlorine chemistry to further investigate their global tropospheric distribution. The measured global average Cl‐VSLS mixing ratios, from 0.2 to 13 km altitude, were 46.6 ppt (CH₂Cl₂), 9.6 ppt (CHCl₃), 7.8 ppt (1,2‐DCA), and 0.84 ppt (C₂Cl₄) measured by the NSF NCAR Trace Organic Analyzer (TOGA) during ATom. Both measurements and model show distinct hemispheric gradients with the mean measured Northern to Southern Hemisphere (NH/SH) ratio of 2 or greater for all four Cl‐VSLS. In addition, the TOGA profiles over the NH mid‐latitudes showed general enhancements in the Pacific basin compared to the Atlantic basin, with up to ∼18 ppt difference for CH₂Cl₂in the mid troposphere. We tagged regional source emissions of CH₂Cl₂and C₂Cl₄in the model and found that Asian emissions dominate the global distributions of these species both at the surface (950 hPa) and at high altitudes (150 hPa). Overall, our results confirm relatively high mixing ratios of Cl‐VSLS in the UTLS region and show that the CESM model does a reasonable job of simulating their global abundance but we also note the uncertainties with Cl‐VSLS emissions and active chlorine sources in the model. These findings will be used to validate future emission inventories and to investigate the fast convective transport of Cl‐VSLS to the UTLS region and their impact on stratospheric ozone. 

Ocean biogeochemistry involves the production and consumption of an array of organic compounds and halogenated trace gases that influence the composition and reactivity of the atmosphere, air quality, and the climate system. Some of these molecules affect tropospheric ozone and secondary aerosol formation and impact the atmospheric oxidation capacity on both regional and global scales. Other emissions undergo transport to the stratosphere, where they contribute to the halogen burden and influence ozone. The oceans also comprise a major sink for highly soluble or reactive atmospheric gases. These issues are an active area of research by the SOLAS (Surface Ocean Lower Atmosphere) community. This article provides a status report on progress over the past decade, unresolved issues, and future research directions to understand the influence of ocean biogeochemistry on gas-phase atmospheric chemistry. Common challenges across the subject area involve establishing the role that biology plays in controlling the emissions of gases to the atmosphere and the inclusion of such complex processes, for example involving the sea surface microlayer, in large-scale global models. 

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. 

Abstract Tropospheric reactive halogens influence the oxidizing capacity of the atmosphere. Although previous studies have shown that iodine exerts the strongest impact on tropospheric ozone concentrations compared to chlorine and bromine, the impact of aerosol iodide recycling back to the gas phase on oxidants has not been estimated prior to this work. Here, we explicitly represent aerosol iodine speciation in a chemical transport model, including soluble organic iodine (SOI), iodate, and iodide, and allow for interconversion among these species. We find that aerosol iodine speciation, interconversion, and recycling substantially affect modeled oxidant abundances. Across model sensitivity studies, tropospheric O_x(the odd‐oxygen family for ozone) and O_z(the odd‐oxygen family for the HO_xfamily, including OH) burdens vary by up to 10% and 5%, respectively. These ranges arise from uncertainties in heterogeneous iodine chemistry, demonstrating a need for future laboratory experiments and field observations in this area.