Observation and modelling of ozone-destructive halogen chemistry in a passively degassing volcanic plume

Acknowledgements. As well as the financial support noted below, the authors would like to acknowledge the following. Computer modelling benefited from access to IDRIS HPC resources (GENCI allocation A007017141) and the IPSL mesoscale computing cen- tre (CICLAD: Calcul Intensif pour le CLimat, l’Atmosphère et la Dynamique). Aircraft measurements were carried out within the Global Mercury Observation System project (GMOS; http://www. gmos.eu, last access: 12 August 2021), and we acknowledge the contribution of the GMOS teams of CNR IIA, Italy, and Helmholtz- Zentrum Geesthacht, Germany. GMOS was financially supported by the European Union within the seventh framework programme (FP-7; project ENV.2010.4.1.3-2). The authors would like to thank Louis Marelle and Jennie Thomas for their assistance with the model development. The model presented in this paper is a devel- opment of work undertaken as part of Luke Surl’s PhD, which was funded by the UK’s Natural Environment Research Council and su- pervised by Deanna Donohoue and Roland von Glasow. The authors would like to thank the two anonymous referees for suggesting var- ious improvements to this paper. Financial support. This paper is a result of a project that has re- ceived funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement no. 800062 as well as ANR Projet de Recherche Collaborative VOLC-HAL-CLIM (Volcanic Halogens: from Deep Earth to Atmospheric Impacts), ANR-18-CE01-0018.Peer reviewedPublisher PD

The coupled chemistry-climate model LMDz-REPROBUS: description and evaluation of a transient simulation of the period 1980–1999

We present a description and evaluation of the Chemistry-Climate Model (CCM) LMDz-REPROBUS, which couples interactively the extended version of the Laboratoire de Météorologie Dynamique General Circulation Model (LMDz GCM) and the stratospheric chemistry module of the REactive Processes Ruling the Ozone BUdget in the Stratosphere (REPROBUS) model. The transient simulation evaluated here covers the period 1980–1999. The introduction of an interactive stratospheric chemistry module improves the model dynamical climatology, with a substantial reduction of the temperature biases in the lower tropical stratosphere. However, at high latitudes in the Southern Hemisphere, a negative temperature bias, that is already present in the GCM version, albeit with a smaller magnitude, leads to an overestimation of the ozone depletion and its vertical extent in the CCM. This in turn contributes to maintain low polar temperatures in the vortex, delay the break-up of the vortex and the recovery of polar ozone. The latitudinal and vertical variation of the mean age of air compares favourable with estimates derived from long-lived species measurements, though the model mean age of air is 1–3 years too young in the middle stratosphere. The model also reproduces the observed "tape recorder" in tropical total hydrogen (=H2O+2×CH4), but its propagation is about 30% too fast and its signal fades away slightly too quickly. The analysis of the global distributions of CH4 and N2O suggests that the subtropical transport barriers are correctly represented in the simulation. LMDz-REPROBUS also reproduces fairly well most of the spatial and seasonal variations of the stratospheric chemical species, in particular ozone. However, because of the Antarctic cold bias, large discrepancies are found for most species at high latitudes in the Southern Hemisphere during the spring and early summer. In the Northern Hemisphere, polar ozone depletion and its variability are underestimated in the simulation

Volcanic sulfate aerosol formation in the troposphere

International audienceThe isotopic composition of volcanic sulfate provides insights into the atmospheric chemical processing of volcanic plumes. First, mass-independent isotopic anomalies quantified by Δ17O and to a lesser extent Δ33S and Δ36S in sulfate depend on the relative importance of different oxidation mechanisms that generate sulfate aerosols. Second, the isotopic composition of sulfate (δ34S and δ18O) could be an indicator of fractionation (distillation/condensation) processes occurring in volcanic plumes. Here we present analyses of O-and S isotopic compositions of volcanic sulfate absorbed on very fresh volcanic ash from nine moderate historical eruptions in the Northern Hemisphere. Most of our volcanic sulfate samples, which are thought to have been generated in the troposphere or in the tropopause region, do not exhibit any significant mass-independent fractionation (MIF) isotopic anomalies, apart from those from an eruption of a Mexican volcano. Coupled to simple chemistry model calculations representative of the background atmosphere, our data set suggests that although H2O2 (a MIF-carrying oxidant) is thought to be by far the most efficient sulfur oxidant in the background atmosphere, it is probably quickly consumed in large dense tropospheric volcanic plumes. We estimate that in the troposphere, at least, more than 90% of volcanic secondary sulfate is not generated by MIF processes. Volcanic S-bearing gases, mostly SO2, appear to be oxidized through channels that do not generate significant isotopically mass-independent sulfate, possibly via OH in the gas phase and/or transition metal ion catalysis in the aqueous phase. It is also likely that some of the sulfates sampled were not entirely produced by atmospheric oxidation processes but came out directly from volcanoes without any MIF anomalies

Statistical estimation of stratospheric particle size distribution by combining optical modelling and lidar scattering measurement

International audienceA method for estimating the stratospheric particle size distribution from multiwavelength lidar measurements is presented. It is based on matching measured and model-simulated backscatter coefficients. The lidar backscatter coefficients measured at the three commonly used wavelengths 355, 532 and 1064 nm are compared to a precomputed look-up table of model-calculated values. The optical model assumes that particles are spherical and that their size distribution is unimodal. This inverse problem is not trivial because the optical model is highly non-linear with a strong sensitivity to the size distribution parameters in some cases. The errors in the lidar backscatter coefficients are explicitly taken into account in the estimation. The method takes advantage of the statistical properties of the possible solution cluster to identify the most probable size distribution parameters. In order to discard model-simulated outliers resulting from the strong non-linearity of the model, solutions farther than one standard deviation of the median values of the solution cluster are filtered out, because the most probable solution is expected to be in the densest part of the cluster. Within the filtered solution cluster, the estimation algorithm minimizes a cost function of the misfit between measurements and model simulations. Two validation cases are presented on Polar Stratospheric Cloud (PSC) events detected above the ALOMAR observatory (69° N – Norway). A first validation is performed against optical particle counter measurements carried out in January 1996. In non-depolarizing regions of the cloud (i.e. spherical particles), the parameters of an unimodal size distribution and those of the optically dominant mode of a bimodal size distribution are quite successfully retrieved, especially for the median radius and the geometrical standard deviation. As expected, the algorithm performs poorly when solid particles drive the backscatter coefficient. A small bias is identified in modelling the refractive index when compared to previous works that inferred PSC type Ib refractive indices. The accuracy of the size distribution retrieval is improved when the refractive index is set to the value inferred in the reference paper. Our results are then compared to values retrieved with another similar method that does not account for the effect of the measurements errors and the non-linearity of the optical model on the likelihood of the solution. The case considered is a liquid PSC observed over northern Scandinavia on January 2005. An excellent agreement is found between the two methods when our algorithm is applied without any statistical filtering of the solution cluster. However, the solution for the geometrical standard deviation appears to be rather unlikely with a value close to unity (σ≈1.04). When our algorithm is applied with solution filtering, a more realistic value of the standard deviation (σ≈1.27) is found. This highlights the importance of taking into account the non linearity of the model together with the lidar errors, when estimating particle size distribution parameters from lidar measurements

Stratospheric Ozone destruction by the Bronze-Age Minoan eruption (Santorini Volcano, Greece).

The role of volcanogenic halogen-bearing (i.e. chlorine and bromine) compounds in stratospheric ozone chemistry and climate forcing is poorly constrained. While the 1991 eruption of Pinatubo resulted in stratospheric ozone loss, it was due to heterogeneous chemistry on volcanic sulfate aerosols involving chlorine of anthropogenic rather than volcanogenic origin, since co-erupted chlorine was scavenged within the plume. Therefore, it is not known what effect volcanism had on ozone in pre-industrial times, nor what will be its role on future atmospheres with reduced anthropogenic halogens present. By combining petrologic constraints on eruption volatile yields with a global atmospheric chemistry-transport model, we show here that the Bronze-Age 'Minoan' eruption of Santorini Volcano released far more halogens than sulfur and that, even if only 2% of these halogens reached the stratosphere, it would have resulted in strong global ozone depletion. The model predicts reductions in ozone columns of 20 to >90% at Northern high latitudes and an ozone recovery taking up to a decade. Our findings emphasise the significance of volcanic halogens for stratosphere chemistry and suggest that modelling of past and future volcanic impacts on Earth's ozone, climate and ecosystems should systematically consider volcanic halogen emissions in addition to sulfur emissions

OH and RO 2 radicals at Dome C (East Antarctica): first observations and assessment of photochemical budget

International audienceMeasurements of OH and total peroxy RO 2 (HO 2 + organic peroxy) radicals were performed in December 2011/January 2012 at the Dome C Concordia station (East Antarctica, 75.1˚S / 123.3˚E) in the frame of the Oxi-dant Production over Antarctic Land and its Export (OPALE) project. The goal of these first on the East Antarctica plateau radical measurements was to estimate the oxidative capacity and assess the role of snow emissions on the radical budget in this part of Antarctica. The OH concentration levels were found to be in general similar to those observed at South Pole. However, based on the analysis of the OH sources and sinks derived from the available measurements of NO x , HONO, HCHO, H 2 O 2 and others, it has been concluded that, in contrast to South Pole, the photolysis of HONO is the major OH source at Dome C site. The role of HONO as the major source of OH is also supported by an excellent correlation of OH with the production rate of OH from the HONO photolysis. The observed diurnal profiles of OH and RO 2 are discussed in relation with boundary dynamics and the variability of photolysis and snow emissions rates

Projecting ozone hole recovery using an ensemble of chemistry-climate models weighted by model performance and independence

Calculating a multi-model mean, a commonly used method for ensemble averaging, assumes model independence and equal model skill. Sharing of model components amongst families of models and research centres, conflated by growing ensemble size, means model independence cannot be assumed and is hard to quantify. We present a methodology to produce a weighted-model ensemble projection, accounting for model performance and model independence. Model weights are calculated by comparing model hindcasts to a selection of metrics chosen for their physical relevance to the process or phenomena of interest. This weighting methodology is applied to the Chemistry-Climate Model Initiative (CCMI) ensemble to investigate Antarctic ozone depletion and subsequent recovery. The weighted mean projects an ozone recovery to 1980 levels, by 2056 with a 95 % confidence interval (2052-2060), 4 years earlier than the most recent study. Perfect-model testing and out-of-sample testing validate the results and show a greater projective skill than a standard multi-model mean. Interestingly, the construction of a weighted mean also provides insight into model performance and dependence between the models. This weighting methodology is robust to both model and metric choices and therefore has potential applications throughout the climate and chemistry-climate modelling communities

Climate change projections and stratosphere–troposphere interaction

Climate change is expected to increase winter rainfall and flooding in many extratropical regions as evaporation and precipitation rates increase, storms become more intense and storm tracks move polewards. Here, we show how changes in stratospheric circulation could play a significant role in future climate change in the extratropics through an additional shift in the tropospheric circulation. This shift in the circulation alters climate change in regional winter rainfall by an amount large enough to significantly alter regional climate change projections. The changes are consistent with changes in stratospheric winds inducing a change in the baroclinic eddy growth rate across the depth of the troposphere. A change in mean wind structure and an equatorward shift of the tropospheric storm tracks relative to models with poor stratospheric resolution allows coupling with surface climate. Using the Atlantic storm track as an example, we show how this can double the predicted increase in extreme winter rainfall over Western and Central Europe compared to other current climate projection

Inter-model comparison of global hydroxyl radical (OH) distributions and their impact on atmospheric methane over the 2000–2016 period

The modeling study presented here aims to estimate how uncertainties in global hydroxyl radical (OH) distributions, variability, and trends may contribute to resolving discrepancies between simulated and observed methane (CH4) changes since 2000. A multi-model ensemble of 14 OH fields was analyzed and aggregated into 64 scenarios to force the offline atmospheric chemistry transport model LMDz (Laboratoire de Meteorologie Dynamique) with a standard CH4 emission scenario over the period 2000–2016. The multi-model simulated global volume-weighted tropospheric mean OH concentration ([OH]) averaged over 2000–2010 ranges between 8:7*10^5 and 12:8*10^5 molec cm-3. The inter-model differences in tropospheric OH burden and vertical distributions are mainly determined by the differences in the nitrogen oxide (NO) distributions, while the spatial discrepancies between OH fields are mostly due to differences in natural emissions and volatile organic compound (VOC) chemistry. From 2000 to 2010, most simulated OH fields show an increase of 0.1–0:3*10^5 molec cm-3 in the tropospheric mean [OH], with year-to-year variations much smaller than during the historical period 1960–2000. Once ingested into the LMDz model, these OH changes translated into a 5 to 15 ppbv reduction in the CH4 mixing ratio in 2010, which represents 7%–20% of the model-simulated CH4 increase due to surface emissions. Between 2010 and 2016, the ensemble of simulations showed that OH changes could lead to a CH4 mixing ratio uncertainty of > 30 ppbv. Over the full 2000–2016 time period, using a common stateof- the-art but nonoptimized emission scenario, the impact of [OH] changes tested here can explain up to 54% of the gap between model simulations and observations. This result emphasizes the importance of better representing OH abundance and variations in CH4 forward simulations and emission optimizations performed by atmospheric inversions

Analysis of the global atmospheric background sulfur budget in a multi-model framework

Sulfate aerosol in the stratosphere is an important climate driver, causing solar dimming in the years after major volcanic eruptions. Hence, a growing number of general circulation models are adapting interactive sulfur and aerosol schemes to improve the representation of relevant chemical processes and associated feedbacks. However, uncertainties of these schemes are not well constrained. Stratospheric sulfate is modulated by natural emissions of sulfur-containing species, including volcanic eruptive, and anthropogenic emissions. Model intercomparisons have examined the effects of volcanic eruptions, whereas the background conditions of the sulfur cycle have not been addressed in a global model intercomparison project. Assessing background conditions in global models allows us to identify model discrepancies as they are masked by large perturbations such as volcanic eruptions, yet may still matter in the aftermath of such a disturbance. Here, we analyze the atmospheric burden, seasonal cycle, and vertical and meridional distribution of the main sulfur species among nine global atmospheric aerosol models that are widely used in the stratospheric aerosol research community. We use observational and reanalysis data to evaluate model results. Overall, models agree that the three dominant sulfur species in terms of burdens (sulfate aerosol, OCS, and SO2) make up about 98 % of stratospheric sulfur and 95 % of tropospheric sulfur. However, models vary considerably in the partitioning between these species. Models agree that anthropogenic emission of SO2 strongly affects the sulfate aerosol burden in the Northern Hemispheric troposphere, while its importance is very uncertain in other regions. The total deposition of sulfur varies among models, deviating by a factor of two, but models agree that sulfate aerosol is the main form in which sulfur is deposited. Additionally, the partitioning between wet and dry deposition fluxes is highly model dependent. We investigate the areas of greatest variability in the sulfur species burdens and find that inter-model variability is low in the tropics and increases towards the poles. Seasonality in the southern hemisphere is depicted very similar among models. Differences are largest in the dynamically active northern hemispheric extratropical region, hence some of the differences could be attributed to the differences in the representation of the stratospheric circulation among underlying general circulation models. This study highlights that the differences in the atmospheric sulfur budget among the models arise from the representation of both chemical and dynamical processes, whose interplay complicates the bias attribution. Several problematic points identified for individual models are related to the specifics of the chemistry schemes, model resolution, and representation of cross-tropopause transport in the extratropics. Further model intercomparison research is needed focusing on the clarification of the reasons for biases, given also the importance of this topic for the stratospheric aerosol injection studies.</p