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1. Changes in Stratosphere‐Troposphere Exchange of Air Mass and Ozone Concentration in CCMI Models From 1960 to 2099

   https://doi.org/10.1029/2023JD038487  

   Wang, Mingcheng; Fu, Qiang (July 2023, Journal of Geophysical Research: Atmospheres)

   Abstract This study investigates changes in stratosphere‐troposphere exchange (STE) of air masses and ozone concentrations from 1960 to 2099 using multiple model simulations from Chemistry Climate Model Initiative (CCMI) under climate change scenario RCP6.0. We employ a lowermost stratosphere mass budget approach with dynamic isentropic surfaces fitted to the tropical tropopause as the upper boundary of lowermost stratosphere. The multi‐model mean (MMM) trends of air mass STEs are all small over all regions, which are within 0.3 (0.1) % decade⁻¹for 1960–2000 (2000–2099). The MMM trends of ozone STE for 1960–2000 are 0.3%, −2.7%, 3.4%, −0.9%, and −2.7% decade⁻¹over the Northern hemisphere (NH) extratropics, Southern hemisphere (SH) extratropics, tropics, extratropics, and globe, respectively. The corresponding ozone STE trends for 2000–2099 are 3.0%, 4.3%, 0.8%, 3.5%, and 4.7% decade⁻¹. Changes in ozone STEs are dominated by ozone concentration changes, driven by climate‐induced changes and ozone‐depleting substance (ODS) changes. For 1960–2000, small changes in ozone STEs in the NH extratropics are due to a cancellation between effects of climate‐induced changes and ODS increases, while the ODS effect dominates in the SH extratropics, leading to a large ozone STE magnitude decrease. Increased ozone transport from tropical troposphere to stratosphere for 1960–2000 is due to increased tropospheric ozone. A decreased global ozone STE magnitude for 1960–2000 was largely caused by ODS‐induced ozone loss that is partly compensated by climate‐induced ozone changes. For 2000–2099, about two‐thirds of global ozone STE magnitude increases are caused by ozone increases in the extratropical lower stratosphere due to climate‐induced changes. The remaining one‐third is caused by ozone recovery due to the phaseout of ODS. 

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2. Calibrating the Tropospheric Air and Ozone Mass

   https://doi.org/10.1029/2025AV001651  

   Prather, Michael J (June 2025, AGU Advances)

   Abstract We divide the atmosphere into distinct spheres based on their physical, chemical, and dynamical traits. In deriving chemical budgets and climate trends, which differ across spheres, we need clearly defined boundaries. Our primary spheres are the troposphere and stratosphere (∼99.9% by mass), and the boundary between them is the tropopause. Every global climate‐weather model has one or more methods to calculate the lapse rate tropopause, but these involve subjective choices and are known to fail near the sub‐tropical jets and polar regions. Age‐of‐air tracers clock the effective time‐distance from the tropopause, allowing unambiguous separation of stratosphere from troposphere in the chaotic jet regions. We apply a global model with synthetic tracer e90 (90‐day e‐folding), focusing on ozone and temperature structures about the tropopause using ozone sonde and satellite observations. We calibrate an observation‐consistent tropopause for e90 using tropics‐plus‐midlatitudes and then apply it globally to calculate total tropospheric air‐mass and tropopause ozone values. The tropopause mixing barrier for the current UCI CTM is identified by a transition in the vertical transport gradient to stratospheric values of 15 days km⁻¹, corresponding to an e90 tropopause at 81 ± 2 ppb with a global tropospheric air mass of 82.2 ± 0.3%. The best e90 tropopause based on sonde pressures is 70–80 ppb; but that for ozone is 80–90 ppb, implying that the CTM tropopause ozone values are too large. This approach of calibrating an age‐of‐air tropopause can be readily applied to other models and possibly used with observed age‐of‐air tracers like sulfur hexafluoride. 

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3. On the atmospheric budget of 1,2-dichloroethane and its impact on stratospheric chlorine and ozone (2002–2020)

   https://doi.org/10.5194/acp-24-13457-2024  

   Hossaini, Ryan; Sherry, David; Wang, Zihao; Chipperfield, Martyn P; Feng, Wuhu; Oram, David E; Adcock, Karina E; Montzka, Stephen A; Simpson, Isobel J; Mazzeo, Andrea; et al (December 2024, Atmospheric Chemistry and Physics)

   Abstract. The chemical compound 1,2-dichloroethane (DCE), or ethylene dichloride, is an industrial very short-lived substance (VSLS) whose major use is as a feedstock in the production chain of polyvinyl chloride (PVC). Like other chlorinated VSLSs, transport of DCE (and/or its atmospheric oxidation products) to the stratosphere could contribute to ozone depletion there. However, despite annual production volumes greatly exceeding those of more prominent VSLSs (e.g. dichloromethane), global DCE observations are sparse; thus, the magnitude and distribution of DCE emissions and trends in its atmospheric abundance are poorly known. In this study, we performed an exploratory analysis of the global DCE budget between 2002 and 2020. Combining bottom-up data on annual production and assumptions around fugitive losses during production and feedstock use, we assessed the DCE source strength required to reproduce atmospheric DCE observations. We show that the TOMCAT/SLIMCAT 3-D chemical transport model (CTM) reproduces DCE measurements from various aircraft missions well, including HIPPO (2009–2011), ATom (2016–2018), and KORUS-AQ (2016), along with surface measurements from Southeast Asia, when assuming a regionally varying production emission factor in the range of 0.5 %–1.5 %. Our findings imply substantial fugitive losses of DCE and/or substantial emissive applications (e.g. solvent use) that are poorly reported. We estimate that DCE's global source increased by ∼ 45 % between 2002 (349 ± 61 Gg yr−1) and 2020 (505 ± 90 Gg yr−1), with its contribution to stratospheric chlorine increasing from 8.2 (± 1.5) to ∼ 12.9 (± 2.4) ppt Cl (where ppt denotes parts per trillion) over this period. DCE's relatively short overall tropospheric lifetime (∼ 83 d) limits, although does not preclude, its transport to the stratosphere, and we show that its impact on ozone is small at present. Annually averaged, DCE is estimated to have decreased ozone in the lower stratosphere by up to several parts per billion (< 1 %) in 2020, although a larger effect in the springtime Southern Hemisphere polar lower stratosphere is apparent (decreases of up to ∼ 1.3 %). Given strong potential for growth in DCE production tied to demand for PVC, ongoing measurements would be of benefit to monitor potential future increases in its atmospheric abundance and its contribution to ozone depletion. 

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4. Lifetimes and timescales of tropospheric ozone

   https://doi.org/10.1525/elementa.2023.00112  

   Prather, Michael J; Zhu, Xin (January 2024, Elem Sci Anth)

   The lifetime of tropospheric O3 is difficult to quantify because we model O3 as a secondary pollutant, without direct emissions. For other reactive greenhouse gases like CH4 and N2O, we readily model lifetimes and timescales that include chemical feedbacks based on direct emissions. Here, we devise a set of artificial experiments with a chemistry-transport model where O3 is directly emitted into the atmosphere at a quantified rate. We create 3 primary emission patterns for O3, mimicking secondary production by surface industrial pollution, that by aviation, and primary injection through stratosphere–troposphere exchange (STE). The perturbation lifetimes for these O3 sources includes chemical feedbacks and varies from 6 to 27 days depending on source location and season. Previous studies derived lifetimes around 24 days estimated from the mean odd-oxygen loss frequency. The timescales for decay of excess O3 varies from 10 to 20 days in northern hemisphere summer to 30 to 40 days in northern hemisphere winter. For each season, we identify a single O3 chemical mode applying to all experiments. Understanding how O3 sources accumulate (the lifetime) and disperse (decay timescale) provides some insight into how changes in pollution emissions, climate, and stratospheric O3 depletion over this century will alter tropospheric O3. This work incidentally found 2 distinct mistakes in how we diagnose tropospheric O3, but not how we model it. First, the chemical pattern of an O3 perturbation or decay mode does not resemble our traditional view of the odd-oxygen family of species that includes NO2. Instead, a positive O3 perturbation is accompanied by a decrease in NO2. Second, heretofore we diagnosed the importance of STE flux to tropospheric O3 with a synthetic “tagged” tracer O3S, which had full stratospheric chemistry and linear tropospheric loss based on odd-oxygen loss rates. These O3S studies predicted that about 40% of tropospheric O3 was of stratospheric origin, but our lifetime and decay experiments show clearly that STE fluxes add about 8% to tropospheric O3, providing further evidence that tagged tracers do not work when the tracer is a major species with chemical feedbacks on its loss rates, as shown previously for CH4. 

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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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