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A lightning parametrisation based on upward cloud ice flux is implemented in a chemistry–climate model (CCM) for the first time. The UK Chemistry and Aerosols model is used to study the impact of these lightning nitric oxide (NO) emissions on ozone. Comparisons are then made between the new ice flux parametrisation and the commonly used, cloud-top height parametrisation. The ice flux approach improves the simulation of lightning and the temporal correlations with ozone sonde measurements in the middle and upper troposphere. Peak values of ozone in these regions are attributed to high lightning NO emissions. The ice flux approach reduces the overestimation of tropical lightning apparent in this CCM when using the cloud-top approach. This results in less NO emission in the tropical upper troposphere and more in the extratropics when using the ice flux scheme. In the tropical upper troposphere the reduction in ozone concentration is around 5–10 %. Surprisingly, there is only a small reduction in tropospheric ozone burden when using the ice flux approach. The greatest absolute change in ozone burden is found in the lower stratosphere, suggesting that much of the ozone produced in the upper troposphere is transported to higher altitudes. Major differences in the frequency distribution of flash rates for the two approaches are found. The cloud-top height scheme has lower maximum flash rates and more mid-range flash rates than the ice flux scheme. The initial Ox (odd oxygen species) production associated with the frequency distribution of continental lightning is analysed to show that higher flash rates are less efficient at producing Ox; low flash rates initially produce around 10 times more Ox per flash than high-end flash rates. We find that the newly implemented lightning scheme performs favourably compared to the cloud-top scheme with respect to simulation of lightning and tropospheric ozone. This alternative lightning scheme shows spatial and temporal differences in ozone chemistry which may have implications for comparison between models and observations, as well as for simulation of future changes in tropospheric ozone.

Understanding the past, present, and future evolution of methane remains a grand challenge. Here we have used a hierarchy of models, ranging from simple box models to a chemistry‐climate model (CCM), UM‐UKCA, to assess the contemporary and possible future atmospheric methane burden. We assess two emission data sets for the year 2000 deployed in UM‐UKCA against key observational constraints. We explore the impact of the treatment of model boundary conditions for methane and show that, depending on other factors, such as CO emissions, satisfactory agreement may be obtained with either of the CH4 emission data sets, highlighting the difficulty in unambiguous choice of model emissions in a coupled chemistry model with strong feedbacks. The feedbacks in the CH4‐CO‐OH system, and their uncertainties, play a critical role in the projection of possible futures. In a future driven by large increases in greenhouse gas forcing, increases in tropospheric temperature drive, an increase in water vapor, and, hence, [OH]. In the absence of methane emission changes this leads to a significant decrease in methane compared to the year 2000. However, adding a projected increase in methane emissions from the RCP8.5 scenario leads to a large increase in methane abundance. This is modified by changes to CO and NOx emissions. Clearly, future levels of methane are uncertain and depend critically on climate change and on the future emission pathways of methane and ozone precursors. We highlight that further work is needed to understand the coupled CH4‐CO‐OH system in order to understand better future methane evolution. Plain Language Summary Methane is an important greenhouse gas and needs to be modeled accurately to understand climate change. We use a combination of modeling approaches to investigate how we could model methane in present day conditions and in the future. We used a simple box model to explore how methane behaves in the atmosphere and interacts with other important species such as OH and CO. We then used a more complex 3‐D model of the whole atmosphere employing a more physically realistic way to treat methane emissions in our model than is normally done. We show that the choice of emissions data set is difficult but that good agreement with observations is possible. The simple model shows how some of the difficulty arises: The different components of the system interact nonlinearly. We go on to use this 3‐D modeling approach to study methane levels in future climate. We show that not only methane emissions but also other factors are important to methane levels, again agreeing with the broad conclusions of our simple model. Methane in the future is highly uncertain and depends on climate, emissions, and the interactions between them, mediated by key chemical species, CO, methane, and OH. Key Points We study methane in present and future climate in a model employing flux‐based treatment of methane emissions We examine the source and importance of feedbacks in the CH4‐CO‐OH system using a 0‐D box model and a 3‐D chemistry‐climate model We examine methane levels in future climate and the role played by climate and emissions changes

The impact of polar stratospheric ozone loss resulting from chlorine activation on polar stratospheric clouds is examined using a pair of model integrations run with the fully coupled chemistry climate model UM-UKCA. Suppressing chlorine activation through heterogeneous reactions is found to produce modelled ozone differences consistent with observed ozone differences between the present and pre-ozone hole period. Statistically significant high-latitude Southern Hemisphere (SH) ozone loss begins in August and peaks in October–November, with > 75% of ozone destroyed at 50 hPa. Associated with this ozone destruction is a > 12 K decrease of the lower polar stratospheric temperatures and an increase of > 6 K in the upper stratosphere. The heating components of this temperature change are diagnosed and it is found that the temperature dipole is the result of decreased short-wave heating in the lower stratosphere and increased dynamical heating in the upper stratosphere. The cooling of the polar lower stratosphere leads, through thermal wind balance, to an acceleration of the polar vortex and delays its breakdown by ~ 2 weeks. A link between lower stratospheric zonal wind speed, the vertical component of the Eliassen–Palm (EP) flux, Fz and the residual mean vertical circulation, w*, is identified. In November and December, increased westerly winds and a delay in the breakup of the polar vortex lead to increases in Fz, indicating increased wave activity entering the stratosphere and propagating to higher altitudes. The resulting increase in wave breaking, diagnosed by decreases to the EP flux divergence, drives enhanced downwelling over the polar cap. Many of the stratospheric signals modelled in this study propagate down to the troposphere, and lead to significant surface changes in December.

Lightning is one of the major natural sources of NOx in the atmosphere. A suite of time slice experiments using a stratosphere-resolving configuration of the Unified Model (UM), containing the United Kingdom Chemistry and Aerosols sub-model (UKCA), has been performed to investigate the impact of climate change on emissions of NOx from lightning (LNOx ) and to highlight its critical impacts on photochemical ozone production and the oxidising capacity of the troposphere. Two Representative Concentration Pathway (RCP) scenarios (RCP4.5 and RCP8.5) are explored. LNOx is simulated to increase in a year-2100 climate by 33% (RCP4.5) and 78% (RCP8.5), primarily as a result of increases in the depth of convection. The total tropospheric chemical odd oxygen production (P(Ox )) increases linearly with increases in total LNOx and consequently, tropospheric ozone burdens of 29 ± 4 Tg(O3 ) (RCP4.5) and 46 ± 4 Tg(O3 ) (RCP8.5) are calculated here. By prescribing a uniform surface boundary concentration for methane in these simulations, methane-driven feedbacks are essentially neglected. A simple estimate of the contribution of the feedback reduces the increase in ozone burden to 24 and 33 Tg(O3 ), respectively. We thus show that, through changes in LNOx , the effects of climate change counteract the simulated mitigation of the ozone burden, which results from reductions in ozone precursor emissions as part of air quality controls projected in the RCP scenarios. Without the driver of increased LNOx , our simulations suggest that the net effect of climate change would be to lower free tropospheric ozone. In addition, we identify large climate-change-induced enhancements in the concentration of the hydroxyl radical (OH) in the tropical upper troposphere (UT), particularly over the Maritime Continent, primarily as a consequence of greater LNOx . The OH enhancement in the tropics increases oxidation of both methane (with feedbacks onto chemistry and climate) and very short-lived substances (VSLS) (with implications for stratospheric ozone depletion). We emphasise that it is important to improve our understanding of LNOx in order to gain confidence in model projections of composition change under future climate.

Naturally produced very short-lived substances (VSLS) account for almost a quarter of the current stratospheric inorganic bromine, Bry. Following VSLS oxidation, bromine radicals (Br and BrO) can catalytically destroy ozone. The extent to which possible increases in surface emissions or transport of these VSLS bromocarbons to the stratosphere could counteract the effect of halogen reductions under the Montreal Protocol is an important policy question. Here, by using a chemistry–climate model, UM-UKCA, we investigate the impact of a hypothetical doubling (an increase of 5 ppt Bry) of VSLS bromocarbons on ozone and how the resulting ozone changes depend on the background concentrations of chlorine and bromine. Our model experiments indicate that for the 5 ppt increase in Bry from VSLS, the ozone decrease in the lowermost stratosphere of the Southern Hemisphere (SH) may reach up to 10% in the annual mean; the ozone decrease in the Northern Hemisphere (NH) is smaller (4–6%). The largest impact on the ozone column is found in the Antarctic spring. There is a significantly larger ozone decrease following the doubling of the VSLS burden under a high stratospheric chlorine background than under a low chlorine background, indicating the importance of the inter-halogen reactions. For example, the decline in the high-latitude, lower-stratospheric ozone concentration as a function of Bry is higher by about 30–40% when stratospheric Cly is ~ 3 ppb (present day), compared with Cly of ~ 0.8 ppb (a pre-industrial or projected future situation). Bromine will play an important role in the future ozone layer. However, even if bromine levels from natural VSLS were to increase significantly later this century, changes in the concentration of ozone will likely be dominated by the decrease in anthropogenic chlorine. Our calculation suggests that for a 5 ppt increase in Bry from VSLS, the Antarctic ozone hole recovery date could be delayed by approximately 6–8 years, depending on Cly levels.

Over the 21st century, changes in CO2 levels, climate and land use are expected to alter the global distribution of vegetation, leading to changes in trace gas emissions from plants, including, importantly, the emissions of isoprene. This, combined with changes in anthropogenic emissions, has the potential to impact tropospheric ozone levels, which above a certain level are harmful to animals and vegetation. In this study we use a biogenic emissions model following the empirical parameterisation of the MEGAN model, with vegetation distributions calculated by the Sheffield Dynamic Global Vegetation Model (SDGVM) to explore a range of potential future (2095) changes in isoprene emissions caused by changes in climate (including natural land use changes), land use, and the inhibition of isoprene emissions by CO2. From the present-day (2000) value of 467 Tg C yr−1, we find that the combined impact of these factors could cause a net decrease in isoprene emissions of 259 Tg C yr−1 (55%) with individual contributions of +78 Tg C yr−1 (climate change), −190 Tg C yr−1 (land use) and −147 Tg C yr−1 (CO2 inhibition). Using these isoprene emissions and changes in anthropogenic emissions, a series of integrations is conducted with the UM-UKCA chemistry-climate model with the aim of examining changes in ozone over the 21st century. Globally, all combined future changes cause a decrease in the tropospheric ozone burden of 27 Tg (7%) from 379 Tg in the present-day. At the surface, decreases in ozone of 6–10 ppb are calculated over the oceans and developed northern hemispheric regions, due to reduced NOx transport by PAN and reductions in NOx emissions in these areas respectively. Increases of 4–6 ppb are calculated in the continental tropics due to cropland expansion in these regions, increased CO2 inhibition of isoprene emissions, and higher temperatures due to climate change. These effects outweigh the decreases in tropical ozone caused by increased tropical isoprene emissions with climate change. Our land use change scenario consists of cropland expansion, which is most pronounced in the tropics. The tropics are also where land use change causes the greatest increases in ozone. As such there is potential for increased crop exposure to harmful levels of ozone. However, we find that these ozone increases are still not large enough to raise ozone to such damaging levels.

We report results from two pairs of chemistry-climate model simulations using the same climate model but different chemical perturbations. In each pair of experiments an ozone change was triggered by a simple change in the chemistry. One pair of model experiments looked at the impact of polar stratospheric clouds (PSCs) and the other pair at the impact of short-lived halogenated species on composition and circulation. The model response is complex with both positive and negative changes in ozone concentration, depending on location. These changes result from coupling between composition, temperature and circulation. Even though the causes of the modelled ozone changes are different, the high latitude Southern Hemisphere response in the lower stratosphere is similar. In both pairs of experiments the high-latitude circulation changes, as evidenced by N2O differences, are suggesting a slightly longer-lasting/stronger stratospheric descent in runs with higher ozone destruction (a manifestation of a seasonal shift in the circulation). We contrast the idealised model behaviour with interannual variability in ozone and N2O as observed by the MIPAS instrument on ENVISAT, highlighting similarities of the modelled climate equilibrium changes to the year 2006–2007 in observations. We conclude that the climate system can respond quite sensitively in its seasonal evolution to small chemical perturbations, that circulation adjustments seen in the model can occur in reality, and that coupled chemistry-climate models allow a better assessment of future ozone and climate change than recent CMIP-type models with prescribed ozone fields.

We document the implementation of the Common Representative Intermediates Mechanism version 2, reduction 5 into the United Kingdom Chemistry and Aerosol model (UKCA) version 10.9. The mechanism is merged with the stratospheric chemistry already used by the StratTrop mechanism, as used in UKCA and the UK Earth System Model, to create a new CRI‐Strat mechanism. CRI‐Strat simulates a more comprehensive treatment of non‐methane volatile organic compounds (NMVOCs) and provides traceability with the Master Chemical Mechanism. In total, CRI‐Strat simulates the chemistry of 233 species competing in 613 reactions (compared to 87 species and 305 reactions in the existing StratTrop mechanism). However, while more than twice as complex than StratTrop, the new mechanism is only 75% more computationally expensive. CRI‐Strat is evaluated against an array of in situ and remote sensing observations and simulations using the StratTrop mechanism in the UKCA model. It is found to increase production of ozone near the surface, leading to higher ozone concentrations compared to surface observations. However, ozone loss is also greater in CRI‐Strat, leading to less ozone away from emission sources and a similar tropospheric ozone burden compared to StratTrop. CRI‐Strat also produces more carbon monoxide than StratTrop, particularly downwind of biogenic VOC emission sources, but has lower burdens of nitrogen oxides as more is converted into reservoir species. The changes to tropospheric ozone and nitrogen budgets are sensitive to the treatment of NMVOC emissions, highlighting the need to reduce uncertainty in these emissions to improve representation of tropospheric chemical composition. Plain Language Summary To understand the climate and predict how it will change in the future, we need to understand its chemical composition—the trace gases and small particles that exist in tiny quantities in the atmosphere. A key tool we use to do this are computer models which simulate the atmosphere and processes within it. Key processes include the formation of ozone, a harmful pollutant and greenhouse gas in the lower atmosphere. However, the chemistry involved in forming ozone is very complicated, so computer simulations of the atmosphere must greatly simplify the chemistry. These simple schemes may introduce errors in the model. We also have much more complex chemical mechanisms which simulate our best understanding of all chemical reactions, but these complex schemes require too much computational power to be used when simulating the whole atmosphere. In this paper, we describe the implementation of a chemical mechanism that sits between these levels of complexity, realistically simulating the formation and destruction of ozone without being too slow to run. We compare this new mechanism against measurements taken of the atmosphere and the preexisting, simpler chemical mechanism and show that the new mechanism greatly enhances the amount of ozone that is produced. Key Points The CRI‐Strat mechanism has been integrated into the United Kingdom Chemistry and Aerosol model, greatly increasing the complexity of volatile organic compound chemistry compared to StratTrop CRI‐Strat simulates higher surface ozone compared to StratTrop due to greater production, but tropospheric ozone burden is similar The ozone and oxidized nitrogen budgets when running with the CRI‐Strat mechanism show high sensitivity to the input non‐methane volatile organic compound emissions

An important source of polar stratospheric clouds (PSCs), which play a crucial role in controlling polar stratospheric ozone depletion, is from the temperature fluctuations induced by mountain waves. However, this formation mechanism is usually missing in chemistry–climate models because these temperature fluctuations are neither resolved nor parameterised. Here, we investigate the representation of stratospheric mountain-wave-induced temperature fluctuations by the UK Met Office Unified Model (UM) at climate scale and mesoscale against Atmospheric Infrared Sounder satellite observations for three case studies over the Antarctic Peninsula. At a high horizontal resolution (4 km) the regional mesoscale configuration of the UM correctly simulates the magnitude, timing, and location of the measured temperature fluctuations. By comparison, at a low horizontal resolution (2.5° × 3.75°) the global climate configuration fails to resolve such disturbances. However, it is demonstrated that the temperature fluctuations computed by a mountain wave parameterisation scheme inserted into the climate configuration (which computes the temperature fluctuations due to unresolved mountain waves) are in relatively good agreement with the mesoscale configuration responses for two of the three case studies. The parameterisation was used to include the simulation of mountain-wave-induced PSCs in the global chemistry–climate configuration of the UM. A subsequent sensitivity study demonstrated that regional PSCs increased by up to 50% during July over the Antarctic Peninsula following the inclusion of the local mountain-wave-induced cooling phase.

Injection of aerosol particles (or their precursors) into the stratosphere to scatter solar radiation back into space has been suggested as a solar-radiation management scheme for the mitigation of global warming. TiO2 has recently been highlighted as a possible candidate particle because of its high refractive index, but its impact on stratospheric chemistry via heterogeneous reactions is as yet unknown. In this work the heterogeneous reaction of airborne sub-micrometre TiO2 particles with N2 O5 has been investigated for the first time, at room temperature and different relative humidities (RH), using an atmospheric pressure aerosol flow tube. The uptake coefficient of N2 O5 onto TiO2 , γ(N2 O5 ), was determined to be ~1.0 × 10-3 at low RH, increasing to ~3 × 10-3 at 60% RH. The uptake of N2 O5 onto TiO2 is then included in the UKCA chemistry-climate model to assess the impact of this reaction on stratospheric chemistry. While the impact of TiO2 on the scattering of solar radiation is chosen to be similar to the aerosol from the Mt Pinatubo eruption, the impact of TiO2 injection on stratospheric N2 O5 is much smaller.