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Volcanoes emit halogens into the atmosphere that undergo complex chemical cycling in plumes and cause destruction of ozone. We present a case study of the Mount Etna plume in the summer of 2012, when the volcano was passively degassing, using aircraft observations and numerical simulations with a new 3D model "WRF-Chem Volcano" (WCV), incorporating volcanic emissions and multi-phase halogen chemistry. Measurements of SO 2 – an indicator of plume intensity – and ozone were made in the plume a few tens of kilometres from Etna, revealing a strong negative correlation between ozone and SO 2 levels. From these observations, using SO 2 as a tracer species, we estimate a mean in-plume ozone loss rate of 1.3×10−5 molecules of O 3 per second per molecule of SO 2. This value is similar to observation-based estimates reported very close to Etna's vents, indicating continual ozone loss in the plume up to at least tens of kilometres downwind. The WCV model is run with nested grids to simulate the plume close to the volcano at 1 km resolution. The focus is on the early evolution of passively degassing plumes aged less than 1 h and up to tens of kilometres downwind. The model is able to reproduce the so-called "bromine explosion": the daytime conversion of HBr into bromine radicals that continuously cycle in the plume. These forms include the radical BrO, a species whose ratio with SO 2 is commonly measured in volcanic plumes as an indicator of halogen ozone-destroying chemistry. The species BrO is produced in the ambient-temperature chemistry, with in-plume BrO / SO 2 ratios on the order of 10−4 mol/mol, similar to those observed previously in Etna plumes. Wind speed and time of day are identified as non-linear controls on this ratio. Sensitivity simulations confirm the importance of near-vent radical products from high-temperature chemistry in initiating the ambient-temperature plume halogen cycling. Heterogeneous reactions that activate bromine also activate a small fraction of the emitted chlorine; the resulting production of chlorine radical Cl strongly enhances the methane oxidation and hence the formation of formaldehyde (HCHO) in the plume. Modelled rates of ozone depletion are found to be similar to those derived from aircraft observations. Ozone destruction in the model is controlled by the processes that recycle bromine, with about three-quarters of this recycling occurring via reactions between halogen oxide radicals. Through sensitivity simulations, a relationship between the magnitude of halogen emissions and ozone loss is established. Volcanic halogen cycling profoundly impacts the overall plume chemistry in the model, notably hydrogen oxide radicals (HO x), nitrogen oxides (NO x), sulfur, and mercury chemistry. In the model, it depletes HO x within the plume, increasing the lifetime of SO 2 and hence slowing sulfate aerosol formation. Halogen chemistry also promotes the conversion of NO x into nitric acid (HNO 3). This, along with the displacement of nitrate out of background aerosols in the plume, results in enhanced HNO 3 levels and an almost total depletion of NO x in the plume. The halogen–mercury model scheme is simple but includes newly identified photo-reductions of mercury halides. With this set-up, the mercury oxidation is found to be slow and in near-balance with the photo-reduction of the plume. Overall, the model findings demonstrate that halogen chemistry has to be considered for a complete understanding of sulfur, HO x , reactive nitrogen, and mercury chemistry and of the formation of sulfate particles in volcanic plumes. [ABSTRACT FROM AUTHOR]

The Atmospheric Chemistry Climate Model Intercomparison Project (ACCMIP) ensemble ozone simulations for the present day from the 2000 decade simulation results are evaluated by a state-of-the-art multi-constituent atmospheric chemical reanalysis that ingests multiple satellite data including the Tropospheric Emission Spectrometer (TES), the Microwave Limb Sounder (MLS), the Ozone Monitoring Instrument (OMI), and the Measurement of Pollution in the Troposphere (MOPITT) for 2005–2009. Validation of the chemical reanalysis against global ozonesondes shows good agreement throughout the free troposphere and lower stratosphere for both seasonal and year-to-year variations, with an annual mean bias of less than 0.9 ppb in the middle and upper troposphere at the tropics and mid-latitudes. The reanalysis provides comprehensive spatiotemporal evaluation of chemistry-model performance that compliments direct ozonesonde comparisons, which are shown to suffer from significant sampling bias. The reanalysis reveals that the ACCMIP ensemble mean overestimates ozone in the northern extratropics by 6–11 ppb while underestimating by up to 18 ppb in the southern tropics over the Atlantic in the lower troposphere. Most models underestimate the spatial variability of the annual mean lower tropospheric concentrations in the extratropics of both hemispheres by up to 70 %. The ensemble mean also overestimates the seasonal amplitude by 25–70 % in the northern extratropics and overestimates the inter-hemispheric gradient by about 30 % in the lower and middle troposphere. A part of the discrepancies can be attributed to the 5-year reanalysis data for the decadal model simulations. However, these differences are less evident with the current sonde network. To estimate ozonesonde sampling biases, we computed model bias separately for global coverage and the ozonesonde network. The ozonesonde sampling bias in the evaluated model bias for the seasonal mean concentration relative to global coverage is 40–50 % over the western Pacific and east Indian Ocean and reaches 110 % over the equatorial Americas and up to 80 % for the global tropics. In contrast, the ozonesonde sampling bias is typically smaller than 30 % for the Arctic regions in the lower and middle troposphere. These systematic biases have implications for ozone radiative forcing and the response of chemistry to climate that can be further quantified as the satellite observational record extends to multiple decades. [ABSTRACT FROM AUTHOR]

Simulations of CO, N2O and CH4 from a coupled chemistry-climate model (CMAM) are compared with satellite measurements from Odin Sub-Millimeter Radiometer (Odin/SMR), Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and Aura Microwave Limb Sounder (Aura/MLS). Pressure-latitude cross-sections and seasonal time series demonstrate thatCMAMreproduces the observed global CO, N2O, and CH4 distributions quite well. Generally, excellent agreement with measurements is found between CO simulations and observations in the stratosphere and mesosphere. Differences between the simulations and the ACE-FTS observations are generally within 30%, and the differences between CMAM results and SMR and MLS observations are slightly larger. These differences are comparable with the difference between the instruments in the upper stratosphere and mesosphere. Comparisons of N2O show that CMAM results are usually within 15% of the measurements in the lower and middle stratosphere, and the observations are close to each other. However, the standard version of CMAM has a low N2O bias in the upper stratosphere. The CMAM CH4 distribution also reproduces the observations in the lower stratosphere, but has a similar but smaller negative bias in the upper stratosphere. The negative bias may be due to that the gravity drag is not fully resolved in the model. The simulated polar CO evolution in the Arctic and Antarctic agrees with the ACE and MLS observations. CO measurements from 2006 show evidence of enhanced descent of air from the mesosphere into the stratosphere in the Arctic after strong stratospheric sudden warmings (SSWs). CMAM also shows strong descent of air after SSWs. In the tropics, CMAM captures the annual oscillation in the lower stratosphere and the semiannual oscillations at the stratopause and mesopause seen in Aura/MLS CO and N2O observations and in Odin/SMR N2O observations. The Odin/SMR and Aura/MLS N2O observations also show a quasi-biennial oscillation (QBO) in the upper stratosphere, whereas, the CMAM does not have QBO included. This study confirms that CMAM is able to simulate middle atmospheric transport processes reasonably well. [ABSTRACT FROM AUTHOR]