Following the Hunga Tonga–Hunga Ha’apai (HTHH) eruption in January 2022, stratospheric ozone depletion was observed in the Southern Hemisphere mid-latitudes and Antarctica during the 2022 austral wintertime and springtime. This eruption injected sulfur dioxide and unprecedented amounts of water vapor into the stratosphere. This work examines and quantifies the chemistry contribution of the volcanic materials to the ozone depletion using chemistry-climate model simulations with nudged meteorology. Simulated 2022 ozone and nitrogen oxides (NOx) anomalies show a good agreement with satellite observations. We find that chemistry only contributes up to 6% and 20% ozone destruction at mid-latitudes wintertime and Antarctic springtime respectively. The majority of the ozone depletion is attributed to the internal variability and dynamical changes forced by the eruption. Both the simulation and observations show a significant NOx reduction associated with the HTHH aerosol plume, indicating the enhanced dinitrogen pentoxide hydrolysis on sulfate aerosol.

Chemistry transport models (CTMs) 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 atmospheric composition by global CTMs. Process-based diagnostics are developed which minimize the spatial and temporal sampling differences between airborne in situ measurements and CTM grid points. The developed diagnostics make use of dynamical and chemical vertical coordinates as a means of highlighting areas where focused model improvement is needed. The chosen process is the chemical impact of the Asian summer monsoon (ASM), where deep convection serves a unique pathway for rapid transport of surface emissions and pollutants to the stratosphere. Two global CTM configurations are examined for their representation of the ASM upper troposphere and lower stratosphere (UTLS), using airborne observations collected over south Asia. Application of the developed diagnostics to the CTMs reveals the limitations of zonally-averaged surface boundary conditions for species with sufficiently short tropospheric lifetimes, and that species whose stratospheric loss rates are dominated by photolysis have excellent agreement compared to that observed. Overall, the diagnostics demonstrate the strength of airborne observations toward improving model predictions, and highlight the utility of highly-resolved CTMs to improve the understanding of reactive transport of anthropogenic pollutants to the stratosphere.

Following the Hunga Tonga–Hunga Ha’apai (HTHH) eruption in January 2022, a significant reduction in stratospheric hydrochloric acid (HCl) was observed in the Southern Hemisphere mid-latitudes during the latter half of 2022, suggesting potential chlorine activation. The objective of this study is to comprehensively understand the substantial loss of HCl in the aftermath of HTHH. Satellite measurements along with a global chemistry-climate model are employed for the analysis. We find strong agreement of 2022 anomalies between the modeled and the measured data. The observed tracer-tracer relations between N2O and HCl indicate a significant role of chemical processing in the observed HCl reduction, especially during the austral winter of 2022. Further examining the roles of chlorine gas-phase and heterogeneous chemistry, we find that heterogeneous chemistry emerges as the primary driver for the chemical loss of HCl, with the reaction between HOBr and HCl on sulfate aerosols identified as the dominant loss process.

Many chemical processes depend non-linearly on temperature. Gravity-wave-induced temperature perturbations have been previously shown to affect atmospheric chemistry, but accounting for this process in chemistry-climate models has been a challenge because many gravity waves have scales smaller than the typical model resolution. Here, we present a method to account for subgrid-scale orographic gravity-wave-induced temperature perturbations on the global scale for the Whole Atmosphere Community Climate Model (WACCM). The method consists of deriving the temperature perturbation amplitude $\hat{T}$ consistent with the model’s subgrid-scale gravity wave parametrization, and imposing $\hat{T}$ as a sinusiodal temperature perturbation in the model’s chemistry solver. Because of limitations in the gravity wave parameterization, scaling factors may be necessary to maintain a realistic wave amplitude. We explore scaling factors between 0.6 and 1 based on comparisons to altitude-dependent $\hat{T}$ distributions in two observational datasets. We probe the impact on the chemistry from the grid-point to global scales, and show that the parametrization is able to represent mountain wave events as reported by previous literature. The gravity waves for example lead to increased surface area densities of stratospheric aerosols. This in turn increases chlorine activation, with impacts on the associated chemical composition. We obtain large local changes in some chemical species (e.g., active chlorine, NOx, N2O5) which are likely to be important for comparisons to airborne or satellite observations, but find that the changes to ozone loss are more modest. This approach enables the chemistry-climate modeling community to account for subgrid-scale gravity wave temperature perturbations in a consistent way.

Simulating whole atmosphere dynamics, chemistry, and physics is computationally expensive. It can require high vertical resolution throughout the middle and upper atmosphere, as well as a comprehensive chemistry and aerosol scheme coupled to radiation physics. An unintentional outcome of the development of one of the most sophisticated and hence computationally expensive model configurations is that it often excludes a broad community of users with limited computational resources. Here, we analyze two configurations of the Community Earth System Model Version 2, Whole Atmosphere Community Climate Model Version 6 (CESM2(WACCM6)) with simplified “middle atmosphere” chemistry at nominal 1 and 2 degree horizontal resolutions. Using observations, a reanalysis, and direct model comparisons, we find that these configurations generally reproduce the climate, variability, and climate sensitivity of the 1 degree nominal horizontal resolution configuration with comprehensive chemistry. While the background stratospheric aerosol optical depth is elevated in the middle atmosphere configurations as compared to the comprehensive chemistry configuration, it is comparable between all configurations during volcanic eruptions. For any purposes other than those needing an accurate representation of tropospheric organic chemistry and secondary organic aerosols, these simplified chemistry configurations deliver reliable simulations of the whole atmosphere that require 35% to 86% fewer computational resources at nominal 1 and 2 degree horizontal resolution, respectively.

The Hunga Tonga-Hunga Ha’apai (HTHH) volcanic eruption in January 2022 injected extreme amounts of water vapor (H2O) and a moderate amount of the aerosol precursor (SO2) into the Southern Hemisphere (SH) stratosphere. The H2O and aerosol perturbations have persisted and resulted in large-scale SH stratospheric cooling, equatorward shift of the Antarctic polar vortex, and slowing of the Brewer-Dobson circulation associated with a substantial ozone reduction in the SH winter midlatitudes. Chemistry-climate model simulations forced by realistic HTHH inputs of H2O and SO2 reproduce the observed stratospheric cooling and circulation effects, demonstrating the observed behavior is due to the volcanic influences. Furthermore, the combination of aerosol transport to polar latitudes and a cold polar vortex enhances springtime Antarctic ozone loss, consistent with observed polar ozone behavior in 2022.

We assess the effective radiative forcing due to ozone-depleting substances using models participating in the Aerosols and Chemistry Model Intercomparison Project (AerChemMIP). A large inter-model spread in this globally averaged quantity necessitates an “emergent constraint” approach whereby we link the radiative forcing to the amount of ozone depletion simulated during 1979-2000, excluding two volcanically perturbed periods. During this period ozone-depleting substances were increasing, and several merged satellite-based climatologies document the ensuing decline of total-column ozone. We use these analyses to come up with effective radiative forcing magnitudes. For all of these satellite climatologies we find an effective radiative forcing outside or on the edge of the previously published “likely” range given by the 5th Assessment Report of IPCC, implying an offsetting effect of ozone depletion and/or other atmospheric feedbacks of -0.4 to -0.25 Wm-2, which is in absolute terms is larger than the previous best estimate of -0.15 Wm-2.

Heterogeneous halogen chemistry plays a dominant role in driving changes in polar chemical composition and ozone depletion. Activation of halogens outside the polar regions may result in depletion of local ozone, along with changes in the chemical budgets of various species in the lower stratosphere (LS). In this paper, both the means and distributions of NO2 measurements from the Stratospheric Aerosol and Gas Experiment III (SAGE3m) are compared to simulations from a coupled climate-chemistry model, in order to better characterize and quantify subpolar heterogeneous halogen chemistry. Observations of NO2 from SAGE3m are found to be drawn from the same distribution as the model simulation with heterogeneous chemistry, but from a different distribution than the simulation without heterogeneous chemistry. Results indicate that heterogeneous chemistry plays a significant role in determining the chemical composition of the subpolar LS and show how analysis of distribution functions can provide useful insights to chemical processes.

Stratospheric dynamics and chemistry can impact the tropospheric climate through changing radiatively active atmospheric constituents and stratosphere-troposphere interactions. The impact of stratospheric dynamics and chemistry on the Last Glacial Maximum (LGM) climate is not well studied and remains an uncertain aspect of glacial-interglacial climate change. Here we perform coupled LGM simulations using the Community Earth System Model version 2 (CESM2), with a high-top atmosphere—the Whole Atmosphere Community Climate Model version 6 with a middle atmosphere chemistry mechanism (WACCM6ma). The CESM2(WACCM6ma) LGM simulations show a weaker stratospheric circulation than the preindustrial, 10–35% less tropospheric ozone and 10–50% more ozone in the lower stratosphere. These stratospheric dynamics and chemistry changes cause slightly colder (by <5%) LGM surface and tropospheric temperatures than parallel simulations using a low-top atmosphere model without active chemistry. The results suggest that stratospheric dynamics and chemistry have little direct effect on the glacial-interglacial climate change.

The Brewer-Dobson Circulation (BDC) determines the distribution of long-lived trac- ers in the stratosphere; therefore, their changes can be used to diagnose changes in the BDC. We evaluate decadal (2005-2018) trends of nitrous oxide (N2O) in two versions of the Whole Atmosphere Chemistry-Climate Model (WACCM) by comparing them with measurements from four Fourier transform infrared (FTIR) ground-based instruments, the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and with a chemistry-transport model (CTM) driven by four different reanalyses. The limited sensitivity of the FTIR instruments can hide negative N2O trends in the mid-stratosphere because of the large increase in the lowermost stratosphere. When applying ACE-FTS measurement sampling on model datasets, the reanalyses from the European Centre for Medium Range Weather Forecast (ECMWF) compare best with ACE-FTS, but the N2O trends are consistently exaggerated. The N2O trends obtained with WACCM disagree with those obtained from ACE-FTS, but the new WACCM version performs better than the previous above the Southern Hemisphere in the stratosphere. Model sensitivity tests show that the decadal N2O trends reflect changes in the stratospheric transport. We further investigate the N2 O Transformed Eulerian Mean (TEM) budget in WACCM and in the CTM simulation driven by the latest ECMWF reanalysis. The TEM analysis shows that enhanced advection affects the stratospheric N2O trends in the Tropics. While no ideal observational dataset currently exists, this model study of N2O trends still provides new insights about the BDC and its changes because of the contribution from relevant sensitivity tests and the TEM analysis.

Using nine chemistry-climate and eight associated no-chemistry models, we investigate the persistence and timing of cold episodes occurring in the Arctic and Antarctic stratosphere during the period 1980-2014. We find systematic differences in behavior between members of these model pairs. In a first group of chemistry models whose dynamical configurations mirror their no-chemistry counterparts, we find an increased persistence of such cold polar vortices, such that these cold episodes both start earlier and last longer, relative to the times of occurrence of the lowest temperatures. Also the date of occurrence of the lowest temperatures, both in the Arctic and the Antarctic, is delayed by 1-3 weeks in chemistry models, versus their no-chemistry counterparts. This behavior exacerbates a widespread problem occurring in most or all models, a delayed occurrence, in the median, of the most anomalously cold day during such cold winters. In a second group of model pairs there are differences beyond just ozone chemistry. In particular, here the chemistry models feature more levels in the stratosphere, a raised model top, and differences in non-orographic gravity wave drag versus their no-chemistry counterparts. Such additional dynamical differences can completely mask the above influence of ozone chemistry. The results point towards a need to retune chemistry-climate models versus their no-chemistry counterparts.

Wave-induced adiabatic mixing in the winter midlatitudes is one of the key processes impacting stratospheric transport. Understanding its strength and structure is vital to understanding the distribution of trace gases and their modulation under a changing climate. age-of-air is often used to understand stratospheric transport, and this study proposes refinements to the vertical age gradient theory of Linz et al. (2021). The theory assumes exchange of air between a well-mixed tropics and a well-mixed extratropics, separated by a transport barrier, quantifying the adiabatic mixing flux across the interface using age-based measures. These assumptions are re-evaluated and a refined framework that includes the effects of meridional tracer gradients is established to quantify the mixing flux. This is achieved, in part, by computing a circulation streamfunction in age-potential temperature coordinates to generate a complete distribution of parcel ages being mixed in the midlatitudes. The streamfunction quantifies the “true” age of parcels mixed between the tropics and the extratropics. Applying the revised theory to an idealized and a comprehensive climate model reveals that ignoring the meridional gradients in age leads to an underestimation of the wave-driven mixing flux. Stronger, and qualitatively similar fluxes are obtained in both models, especially in the lower-to-middle stratosphere. While the meridional span of adiabatic mixing in the two models exhibits some differences, they show that the deep tropical pipe, i.e. latitudes equatorward of 15$^{\circ}$ barely mix with older midlatitude air. The novel age-potential temperature circulation can be used to quantify additional aspects of stratospheric transport.