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This study explores our ability to simulate the atmospheric chemistry stemming from isoprene emissions in pristine and polluted regions of the Amazon basin. We confront two atmospheric chemistry models – a global, Eulerian chemistry-climate model (UM-UKCA) and a trajectory-based Lagrangian model (CiTTyCAT) – with recent airborne measurements of atmospheric composition above the Amazon made during the SAMBBA campaign of 2012. The simulations with the two models prove relatively insensitive to the chemical mechanism employed; we explore one based on the Mainz Isoprene Mechanism, and an updated one that includes changes to the chemistry of first generation isoprene nitrates (ISON) and the regeneration of hydroxyl radicals via the formation of hydroperoxy-aldehydes (HPALDS) from hydroperoxy radicals (ISO2). In the Lagrangian model, the impact of increasing the spatial resolution of trace gas emissions employed from 3.75° × 2.5° to 0.1° × 0.1° varies from one flight to another, and from one chemical species to another. What consistently proves highly influential on our simulations, however, is the model framework itself – how the treatment of transport, and consequently mixing, differs between the two models. The lack of explicit mixing in the Lagrangian model yields variability in atmospheric composition more reminiscent of that exhibited by the measurements. In contrast, the combination of explicit (and implicit) mixing in the Eulerian model removes much of this variability but yields better agreement with the measurements overall. We therefore explore a simple treatment of mixing in the Lagrangian model that, drawing on output from the Eulerian model, offers a compromise between the two models. We use this Lagrangian/Eulerian combination, in addition to the separate Eulerian and Lagrangian models, to simulate ozone at a site in the boundary layer downwind of Manaus, Brazil. The Lagrangian/Eulerian combination predicts a value for an AOT40-like accumulated exposure metric of around 1000 ppbv h, compared to just 20 ppbv h with the Eulerian model. The model framework therefore has considerable bearing on our understanding of the frequency at which, and the duration for which, the rainforest is exposed to damaging ground-level ozone concentrations.

Ozone (O3) isopleths describe the nonlinear responses of O3 concentrations to changes in nitrogen oxides (NOX) and volatile organic compounds (VOCs) and thus are pivotal to the determination of O3 control requirements. In this study, we innovatively use the Community Multiscale Air Quality model with the high-order decoupled direct method (CMAQ-HDDM) to simulate O3 pollution of China in 2017 and derive O3 isopleths for individual cities. Our simulation covering the entire China Mainland suggests severe O3 pollution as 97% of the residents experienced at least 1 day, in 2017, in excess of Chinese Level-II Ambient Air Quality Standards for O3 as 160 μg·m-3 (81.5 ppbV equally). The O3 responses to emissions of precursors vary widely across individual cities. Densely populated metropolitan areas such as Jing-Jin-Ji, Yangtze River Delta, and Pearl River Delta are following NOX-saturated regimes, where a small amount of NOX reduction increases O3. Ambient O3 pollution in the eastern region generally is limited by VOCs, while in the west by NOX. The city-specific O3 isopleths generated in this study are instrumental in forming hybrid and differentiated strategies for O3 abatement in China.

Accurately simulating the geographical distribution and temporal variability of global surface ozone has long been one of the principal components of chemistry-climate modelling. However, the simulation outcomes have been reported to vary significantly as a result of the complex mixture of uncertain factors that control the tropospheric ozone budget. Settling the cross-model discrepancies to achieve higher accuracy predictions of surface ozone is thus a task of priority, and methods that overcome structural biases in models going beyond naïve averaging of model simulations are urgently required. Building on the Coupled Model Intercomparison Project Phase 6 (CMIP6), we have transplanted a conventional ensemble learning approach, and also constructed an innovative 2-stage enhanced space-time Bayesian neural network to fuse an ensemble of 57 simulations together with a prescribed ozone dataset, both of which have realised outstanding performances (R2 > 0.95, RMSE < 2.12 ppbv). The conventional ensemble learning approach is computationally cheaper and results in higher overall performance, but at the expense of oceanic ozone being overestimated and the learning process being uninterpretable. The Bayesian approach performs better in spatial generalisation and enables perceivable interpretability, but induces heavier computational burdens. Both of these multi-stage machine learning-based approaches provide frameworks for improving the fidelity of composition-climate model outputs for uses in future impact studies.

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.

The distribution of ozone in the atmosphere is relevant for air pollution and radiative forcing. This distribution features complex spatial and temporal variability, set by balances between chemical production, loss processes, and advection. At present, the way in which ozone comparison regions are defined relies on somewhat arbitrarily drawn boundaries. In an effort to develop a more general, data-derived method for defining coherent regimes of ozone structure, we apply an unsupervised classification technique called Gaussian Mixture Modelling (GMM). We apply GMM to the output from the UKESM1 coupled climate model, including the historical run and two of the future climate projections. GMM identifies different ozone profile classes without using any latitude or longitude information, thereby highlighting coherent ozone structure regimes. We determine each of the model data set contains 9 groups of unique vertical classes. The classes depend on latitude, even though GMM was not given any latitude information. Polar and subpolar classes show low tropopause and low tropospheric ozone, and the tropical classes have high tropopause. Northern hemisphere high latitude classes have higher stratospheric ozone than southern hemisphere high latitude classes. We analyze how the spatial extent of the classes changes under different scenarios by comparing classes in SSP126 and SSP585 with a historical simulation. This work suggests that GMM may be a useful method for identifying coherent ozone regimes for comparing different model results and observational data.

A grand challenge in the field of chemistry-climate modelling is to understand the connection between anthropogenic emissions, atmospheric composition and the radiative forcing of trace gases and aerosols. The AerChemMIP model intercomparison project, part of CMIP6, focuses on calculating the radiative forcing of gases and aerosol particles over the period 1850 to 2100. We present an analysis of the trends in tropospheric ozone budget in the UKESM1 and other models from CMIP6 experiments. We discuss these trends in terms of chemical production and loss of ozone as well as physical processes such as transport and deposition. Where possible, AerChemMIP attribution experiments such as histSST-piCH4, will be used to quantify the effect of individual emissions and forcing changes on the historical ozone burden and budget. For future experiments, we focus on analogous experiments from the SSP3-70 scenario, a ‘regional rivalry’ shared socioeconomic pathway involving significant emissions changes.

Methane (CH4), the second most important greenhouse gas in terms of radiative forcing, is on the rise; but there are extensive opportunities for mitigation with existing technologies. Anthropogenic emissions account for around 60% of the global methane source, and the recent atmospheric methane growth rate puts us on a trajectory comparable to the most extreme future methane scenarios in the sixth Coupled Model Intercomparison Project (CMIP6). We use a new methane emissions-driven configuration of the UK Earth System Model (UKESM1) to explore the role of anthropogenic methane in the earth system. The full methane cycle is represented, including surface deposition, chemistry and interactive wetland emissions. As a baseline scenario we used Shared Socioeconomic Pathway 3-7.0 (SSP3-7.0) – the highest methane emissions scenario in CMIP6. In an idealised experiment, all anthropogenic methane emissions were instantaneously stopped from 2015 onwards in a coupled atmosphere-ocean simulation running from 2015-2050, to make a net-zero anthropogenic methane emissions scenario. Within a decade, significant changes can be seen in atmospheric composition and climate, compared to SSP3-7.0. The atmospheric methane burden declines to below pre-industrial levels within 12 years, and by the late 2030s reaches a constant level around 44% below that of the present day (2015). The tropospheric ozone burden and surface mean ozone concentrations decreased by 12% and 15% respectively by 2050 – key in terms of limiting global warming as well as improving air quality and human health. By 2050 the net-zero anthropogenic methane scenario results in a global mean surface temperature (GMST) 1˚C lower than the baseline, a significant value in the context of climate goals such as the Paris Agreement. Through decomposition of the radiation budget, the change in climate can be directly attributed to the reduction in methane and indirectly to the resulting changes in ozone, clouds and ozone precursors such as CO. In addition, the changes in climate result in impacts on the interactive wetland emissions via changes in temperature and wetland extent, highlighting the coupled nature of methane in the earth system. Cessation of anthropogenic methane emissions has profound impacts on near-term warming and on tropospheric ozone, but ultimately cannot single-handedly achieve the necessary reductions for meeting Paris goals.

We present the first incorporation and evaluation of the Common Representative Intermediates version 2.2 chemistry mechanism, CRI v2.2, for use in the United Kingdom Earth System Model (UKESM1). Tuned against the MCM v3.3.1, the CRI v2.2 mechanism builds on the previous CRI version, CRI v2.1, in UKESM1 (Archer-Nicholls et al., 2020) by updating isoprene chemistry and offers a more comprehensive description of tropospheric chemistry than the standard chemistry mechanism STRAT-TROP (ST).CRI v2.2 adds state-of-the-art isoprene chemistry with the introduction of HOx-recycling via the isoprene peroxy radical isomerisation pathway, making UKESM1 one of the first CMIP6 models to include this important chemistry. HOx-recycling has noticeable effects on oxidants in regions with large emissions of biogenic volatile organic compounds (BVOCs). Low altitude OH in tropical forested regions increases by 75-150% relative to ST, reducing the existing model low bias compared to observations. Consequently, isoprene surface mixing ratios decrease considerably (25-40%), significantly improving the model high bias relative to ST. Methane lifetime decreases by 2% and tropospheric ozone burden increases by 4%. Aerosol processes also differ between CRI v2.2 and ST, resulting in changes to the size and number distributions. Relative to ST, CRI v2.2 simulates an 8% decrease in the sulphate aerosol burden with 20% decreases in the nucleation and Aitken modes. By contrast, the secondary organic aerosol (SOA) nucleation mode burden increases by 11%. Globally, the average nucleation and Aitken mode aerosol number concentrations decrease by 20%.The differences in aerosol and gas phase chemistry between CRI v2.2 and ST are likely to have impacts on the radiation budget. We plan to use CRI v2.2 and ST to investigate the influence that the chemical mechanism has on the simulated chemistry-climate feedbacks from BVOCs. In addition, CRI v2.2 will serve as the basis for the addition of a scheme describing the formation of highly oxygenated organic molecules (HOMs) from BVOCs, facilitating a semi-explicit mechanism for new particle formation from organic species.

Stratospheric ozone projections in the tropics, modeled using the UKESM1 Earth system model, are explored under different Shared Socioeconomic Pathways (SSPs). Consistent with other studies, it is found that tropical stratospheric column ozone does not return to 1980s values by the end of the 21st century under any SSP scenario as increased ozone mixing ratios in the tropical upper stratosphere are offset by continued ozone decreases in the tropical lower stratosphere. Stratospheric column ozone is projected to be largest under SSP scenarios with the smallest change in radiative forcing, and smallest for SSP scenarios with larger radiative forcing, consistent with a faster Brewer-Dobson circulation at high greenhouse gas loadings. This study explores the use of machine learning (ML) techniques to make accurate, computationally inexpensive projections of tropical stratospheric column ozone. Four ML techniques are investigated: Ridge regression, Lasso regression, Random Forests and Extra Trees. All four techniques investigated here are able to make projections of future tropical stratospheric column ozone which agree well with those made by the UKESM1 Earth system model, often falling within the ensemble spread of UKESM1 simulations for a broad range of SSPs. However, all techniques struggle to make accurate projects for the final decades of the SSP5-8.5 scenario. Accurate projections can only be achieved when the ML methods are trained on sufficient data, including both historical and future simulations. When trained only on historical data, the projections made using models based on ML techniques fail to accurately predict tropical stratospheric ozone changes. Results presented here indicate that, when sufficiently trained, ML models have the potential to make accurate, computationally inexpensive projections of tropical stratospheric column ozone. Further development of these models may reduce the computational burden placed on fully coupled chemistry-climate and Earth system models and enable the exploration of tropical stratospheric column ozone recovery under a much broader range of future emissions scenarios.

Funder: Tsinghua University Initiative Scientific Research Program, Funder: National Centre for Atmospheric Science; doi: http://dx.doi.org/10.13039/501100000662, Funder: Met Office; doi: http://dx.doi.org/10.13039/501100000847, The reliability of air quality simulations has a strong dependence on the input emissions inventories, which are associated with various sources of uncertainties, particularly in regions undergoing rapid emission changes where inventories can be ‘out of date’ almost as soon as they are compiled. This work provides a new methodology for updating emissions inventories by source sector using air quality ensemble simulations and observations from a dense monitoring network. It is adopted to determine the short-term trends in carbon monoxide (CO) emissions, an important pollutant and precursor to tropospheric ozone, in a study area centred around Beijing following the implementation of clean air policies. We sample the uncertainties associated with using an a priori emissions inventory for the year 2013 in air quality simulations of 2016, using an atmospheric dispersion model combined with a perturbed emissions ensemble (PEE), which is constructed based on expert-elicited uncertainty ranges for individual source sectors in the inventory. By comparing the simulation outputs with observational constraints, we are able to constrain the emissions of key source sectors relative to those in the a priori emissions inventory. From 2013 to 2016, we find a 44–88% reduction in the transport sector emissions (0.92–4.4×105 Mg in 2016) and a minimum 61% decrease in residential sector emissions (

Surface ozone is a major pollutant threatening public health, agricultural production and natural ecosystems. While measures to improve air quality in megacities such as Delhi are typically aimed at reducing levels of particulate matter (PM), ozone could become a greater threat if these measures focus on PM alone, as some air pollution mitigation steps can actually lead to an increase in surface ozone. A better understanding of the factors controlling ozone production in Delhi and the impact that PM mitigation measures have on ozone is therefore critical for improving air quality. Here, we combine in situ observations and model analysis to investigate the impact of PM reduction on the non-linear relationship between volatile organic compounds (VOC), nitrogen oxides (NOx) and ozone. In situ measurements of NOx, VOC, and ozone were conducted in Delhi during the APHH-India programme in summer (June) and winter (November) 2018. We observed hourly averaged ozone concentrations in the city of up to 100 ppbv in both seasons. We performed sensitivity simulations with a chemical box model to explore the impacts of PM on the non-linear VOC-NOx-ozone relationship in each season through its effect on aerosol optical depth (AOD). We find that ozone production is limited by VOC in both seasons, and is particularly sensitive to solar radiation in winter. Reducing NOx alone increases ozone, such that a 50% reduction in NOx emissions leads to 10-50% increase in surface ozone. In contrast, reducing VOC emissions can reduce ozone efficiently, such that a 50% reduction in VOC emissions leads to ∼60% reduction in ozone. Reducing PM alone also increases ozone, especially in winter, by reducing its dimming effects on photolysis, such that a 50% reduction in AOD can increase ozone by 25% and it also enhances VOC-limitation. Our results highlight the importance of reducing VOC emissions alongside PM to limit ozone pollution, as well as benefitting control of PM pollution through reducing secondary organic aerosol. This will greatly benefit the health of citizens and the local ecosystem in Delhi, and could have broader application for other megacities characterized by severe PM pollution and VOC-limited ozone production. This journal is

We present an assessment of the impacts on atmospheric composition and radiative forcing of short‐lived pollutants following a worldwide decrease in anthropogenic activity and emissions comparable to what has occurred in response to the COVID‐19 pandemic, using the global composition‐climate model United Kingdom Chemistry and Aerosols Model (UKCA). Emission changes reduce tropospheric hydroxyl radical and ozone burdens, increasing methane lifetime. Reduced SO2 emissions and oxidizing capacity lead to a decrease in sulfate aerosol and increase in aerosol size, with accompanying reductions to cloud droplet concentration. However, large reductions in black carbon emissions increase aerosol albedo. Overall, the changes in ozone and aerosol direct effects (neglecting aerosol‐cloud interactions which were statistically insignificant but whose response warrants future investigation) yield a radiative forcing of −33 to −78 mWm−2. Upon cessation of emission reductions, the short‐lived climate forcers rapidly return to pre‐COVID levels; meaning, these changes are unlikely to have lasting impacts on climate assuming emissions return to pre‐intervention levels., Key Points Emission reductions are likely to have led to a global reduction in short‐lived climate forcers and tropospheric oxidizing capacityReductions in O3 and aerosol from both lower emissions and decreased sulfate oxidation resulted in a net negative radiative forcingThe radiative impacts are small and short‐lived. Longer term climate impacts must come through future sustained emission reductions

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., Key Points We study methane in present and future climate in a model employing flux‐based treatment of methane emissionsWe 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 modelWe examine methane levels in future climate and the role played by climate and emissions changes

The 1257 CE eruption of Mount Samalas (Indonesia) is the source of the largest stratospheric injection of volcanic gases in the Common Era. Sulfur dioxide emissions produced sulfate aerosols that cooled Earth's climate with a range of impacts on society. The coemission of halogenated species has also been speculated to have led to wide-scale ozone depletion. Here we present simulations from HadGEM3-ES, a fully coupled Earth system model, with interactive atmospheric chemistry and a microphysical treatment of sulfate aerosol, used to assess the chemical and climate impacts from the injection of sulfur and halogen species into the stratosphere as a result of the Mt. Samalas eruption. While our model simulations support a surface air temperature response to the eruption of the order of -1°C, performing well against multiple reconstructions of surface temperature from tree-ring records, we find little evidence to support significant injections of halogens into the stratosphere. Including modest fractions of the halogen emissions reported from Mt. Samalas leads to significant impacts on the composition of the atmosphere and on surface temperature. As little as 20% of the halogen inventory from Mt. Samalas reaching the stratosphere would result in catastrophic ozone depletion, extending the surface cooling caused by the eruption. However, based on available proxy records of surface temperature changes, our model results support only very minor fractions (1%) of the halogen inventory reaching the stratosphere and suggest that further constraints are needed to fully resolve the issue.

Tropospheric ozone (O3) can adversely affect human health and environmental ecosystems and it is therefore vitally important to understand its formation pathways from both natural and anthropogenic precursors. Background O3 levels in the Northern Hemisphere have increased by more than a factor of two over the last century and it is believed that this increase is strongly tied to the increase in and distribution of anthropogenic nitrogen oxide (N0x) emissions. This is important as the changing level of O3 in the background troposphere impacts the ability of countries downwind to achieve their air quality standards.As part of the NERC funded North Atlantic Climate System Integrated Study (ACSiS) and Methane Observations and Yearly Assessments (MOYA) projects, multiple research flights have taken place over the North Atlantic Ocean, spanning an area from 55oN to 12oN and 8oW to 25oW using the UK’s large research aircraft (The Facility for Airborne Atmospheric Measurements – FAAM). Flights took place in all seasons from 2017 – 2020. A variety of gas and aerosol measurements were made, including NOx, O3, CO and a range of VOCs and an overview of the data is presented here. Measurements were taken in a range of air masses, including biomass burning outflow from West Africa, urban outflow from Europe and emissions from the busy shipping lanes to the West of Portugal.Data was analysed to assess O3 formation from the different emission sources, in particular examining the difference between anthropogenic and natural emissions. In addition, the output of regional chemistry models is compared to the data in order to assess the performance of the models in predicting O3 and its precursors.

Formaldehyde is a key intermediate in photochemical oxidation of volatile organic compounds in the troposphere and is also directly emitted by a range of sources, including biomass burning and fuel combustion. Airborne measurements of formaldehyde have therefore been used to investigate oxidation in biomass burning (BB) plumes intercepted during the Methane Observations and Yearly Assessments (MOYA) campaign. The MOYA campaign took place January/February 2019 in Uganda and Zambia and mixing ratios of formaldehyde were obtained using the University of Leeds formaldehyde Laser Induced Fluorescence (LIF) instrument. A range of air masses were intercepted including multiple near-field biomass burning (BB) plumes, with up to 140 ppb of formaldehyde observed, and urban emission plumes from the capital city of Kampala in Uganda, where up to 7 ppb of formaldehyde was measured. Formaldehyde emission factors have been calculated for Ugandan BB (1.20 ± 0.23 g kg-1) which agree well with literature (1.23 ± 0.65 g kg-1) for Savannah combustion. Production of formaldehyde as a function of plume age has also been investigated in order to discriminate direct emission from photochemical formation in BB plumes. BB plumes were also intercepted during other aircraft campaigns several days downwind of emission such as a plume transported from Canadian wildfires observed in the North Atlantic during ACSIS-5/ARNA-1 where levels of up to 18.30 ppb were detected, indicative of sustained photochemical oxidation within the plume. Comparison of urban, near-field BB and far-field BB plumes provides a variety of environments and photochemical ages to test our understanding of combustion oxidation processes.

We study the evolution of tropospheric ozone over the period 1979-2010 using a chemistry-climate model employing a stratosphere-troposphere chemistry scheme. By running with specified dynamics, the key feedback of composition on meteorology is constrained, isolating the chemical response. By using historical forcings and emissions representative, interactions between processes are realistically represented. We use the model to ask how the ozone responds over time and to investigate model responses, sensitivities, feedbacks and trends. We find that the CFC-driven decrease in stratospheric ozone plays a significant role in the tropospheric ozone burden. Over the period 1979-1994, the decline in transport of ozone from the stratosphere partially offsets an emissions-driven increase in tropospheric ozone production. From 1994-2010, stratospheric ozone recovery, and a levelling off in emissions, effect a small increase in the tropospheric ozone burden. These results have implications for the impact of future stratospheric ozone recovery on air quality and radiative forcing.

In this study, we show using a state-of-the-art Earth system model, UKESM1, that emissions and climate scenario depending, there could be large changes in surface ozone by the end of the twenty-first century, with unprecedentedly large increases over South and East Asia. We also show that statistical modelling of the trends in future ozone works well in reproducing the model output between 1900 and 2050. However, beyond 2050, and especially under large climate change scenarios, the statistical model results are in poorer agreement with the fully interactive Earth system model output. This suggests that additional processes occurring in the Earth system model such as changes in the production of ozone at higher temperatures or changes in the influx of ozone from the stratosphere, which are not captured by the statistical model, have a first order impact on the evolution of surface ozone over the twenty-first century. We show in a series of idealized box model simulations, with two different chemical schemes, that changes in temperature lead to diverging responses between the schemes. This points at the chemical mechanisms as being a source of uncertainty in the response of ozone to changes in temperature, and so climate, in the future. This underscores the need for more work to be performed to better understand the response of ozone to changes in temperature and constrain how well this relationship is simulated in models. This article is part of a discussion meeting issue ‘Air quality, past present and future’.

Our understanding of the processes that control the burden and budget of tropospheric ozone has changed dramatically over the last 60 years. Models are the key tools used to understand these changes, and these underscore that there are many processes important in controlling the tropospheric ozone budget. In this critical review, we assess our evolving understanding of these processes, both physical and chemical. We review model simulations from the International Global Atmospheric Chemistry Atmospheric Chemistry and Climate Model Intercomparison Project and Chemistry Climate Modelling Initiative to assess the changes in the tropospheric ozone burden and its budget from 1850 to 2010. Analysis of these data indicates that there has been significant growth in the ozone burden from 1850 to 2000 (approximately 43 ± 9%) but smaller growth between 1960 and 2000 (approximately 16 ± 10%) and that the models simulate burdens of ozone well within recent satellite estimates. The Chemistry Climate Modelling Initiative model ozone budgets indicate that the net chemical production of ozone in the troposphere plateaued in the 1990s and has not changed since then inspite of increases in the burden. There has been a shift in net ozone production in the troposphere being greatest in the northern mid and high latitudes to the northern tropics, driven by the regional evolution of precursor emissions. An analysis of the evolution of tropospheric ozone through the 21st century, as simulated by Climate Model Intercomparison Project Phase 5 models, reveals a large source of uncertainty associated with models themselves (i.e., in the way that they simulate the chemical and physical processes that control tropospheric ozone). This structural uncertainty is greatest in the near term (two to three decades), but emissions scenarios dominate uncertainty in the longer term (2050–2100) evolution of tropospheric ozone. This intrinsic model uncertainty prevents robust predictions of near-term changes in the tropospheric ozone burden, and we review how progress can be made to reduce this limitation.

The chemical environments of young planets are assumed to be largely influenced by impacts of bodies lingering on unstable trajectories after the dissolution of the protoplanetary disk. We explore the chemical consequences of impacts within the context of reducing planetary atmospheres dominated by carbon monoxide, methane and molecular nitrogen. A terawatt high-power laser was selected in order to simulate the airglow plasma and blast wave surrounding the impactor. The chemical results of these experiments are then applied to a theoretical atmospheric model. The impact simulation results in substantial volume mixing ratios within the reactor of 5% hydrogen cyanide (HCN), 8% acetylene (C$_2$H$_2$), 5% cyanoacetylene (HC$_3$N) and 1% ammonia (NH$_3$). These yields are combined with estimated impact rates for the Early Earth to predict surface boundary conditions for an atmospheric model. We show that impacts might have served as sources of energy that would have led to steady-state surface quantities of 0.4% C$_2$H$_2$, 400 ppm HCN and 40 ppm NH$_3$. We provide simulated transit spectra for an Earth-like exoplanet with this reducing atmosphere during and shortly after eras of intense impacts. We predict that acetylene is as observable as other molecular features on exoplanets with reducing atmospheres that have recently gone through their own `Heavy Bombardments', with prominent features at 3.05 $\mu$m and 10.5 $\mu$m., Comment: 26 pages, 12 figures, 2 tables, accepted for publication by The Astrophysical Journal

The amount of dioxygen (O2) in the atmosphere may have varied from as little as 10 % to as high as 35 % during the Phanerozoic eon (541 Ma–Present). These changes in the amount of O2 are large enough to have lead to changes in atmospheric mass, which may alter the radiative budget of the atmosphere, leading to this mechanism being invoked to explain discrepancies between climate model simulations and proxy reconstructions of past climates. Here we present the first fully 3D numerical model simulations to investigate the climate impacts of changes in O2 during different climate states using the HadGEM3-AO and HadCM3-BL models. We show that simulations with an increase in O2 content result in increased global mean surface air temperature under conditions of a pre-industrial Holocene climate state, in agreement with idealised 1D and 2D modelling studies. We demonstrate the mechanism behind the warming is complex and involves trade-off between a number of factors. Increasing atmospheric O2 leads to a reduction in incident shortwave radiation at Earth's surface due to Rayleigh scattering, a cooling effect. However, there is a competing warming effect due to an increase in the pressure broadening of greenhouse gas absorption lines and dynamical feedbacks, which alter the meridional heat transport of the ocean, warming polar regions and cooling tropical regions. Case studies from past climates are investigated using HadCM3-BL which show that in the warmest climate states, increasing oxygen may lead to a temperature decrease, as the equilibrium climate sensitivity is lower. For the Maastrichtian (72.1–66.0 Ma), increasing oxygen content leads to a better agreement with proxy reconstructions of surface temperature at that time irrespective of the carbon dioxide content. For the Asselian (298.9–295.0 Ma), increasing oxygen content leads to a warmer global mean surface temperature and reduced carbon storage on land, suggesting that high oxygen content may have been a contributing factor in preventing a Snowball Earth during this period of the early Permian. These climate model simulations reconcile the surface temperature response to oxygen content changes across the hierarchy of model complexity and highlight the broad range of Earth system feedbacks that need to be accounted for when considering the climate response to changes in atmospheric oxygen content.

An intercomparison has been set up to study the representation of the atmospheric chemistry of the pre-industrial troposphere in earth system and other global tropospheric chemistry-transport models. The intercomparison employed a constrained box model and utilised tropospheric trace gas composition data for the pre-industrial times at ninety mid-latitude surface locations. Incremental additions of four organic compounds: methane, ethane, acetone and propane, were used to perturb the constrained box model and generate responses in hydroxyl radicals and tropospheric ozone at each location and with each chemical mechanism. Although the responses agreed well across the chemical mechanisms from the selected earth system and other global tropospheric chemistry-transport models, there were differences in the detailed responses between the chemical mechanisms that could be tracked down by sensitivity analysis to differences in the representation of C1–C3 chemistry. Inter-mechanism ranges in NOx compensation points were about 0.17 ± 0.12 when expressed relative to the inter-mechanism average. Monte Carlo uncertainty analysis carried out with a single chemical mechanism put the intra-mechanism range a factor of three higher at 0.50 ± 0.12. Similar differences between inter-mechanism and intra-mechanism ranges were found for hydroxyl radical depletion but were up to a factor of six wider for ozone formation from incremental additions of organic compounds. The cause of the discrepancies between the inter- and intra-mechanism ranges was found to be the large uncertainties that are present in the laboratory determinations of the rate coefficients and product channel branching ratios of some key chemical reactions involving organic peroxy radicals and hydroperoxides. Whilst these large uncertainties are present in the laboratory determinations, there will be irreducible uncertainties in the predictions from the earth system and other chemistry-transport models of methane and tropospheric ozone trends since pre-industrial times and hence their contributions to the radiative forcing of climate change. Further definitive laboratory studies of the reaction rates and product yields of the reactions of the simple organic peroxy radicals and hydroperoxides are required to resolve and reduce current uncertainties in earth system and chemistry-transport model predictions.

The atmospheric global budget and distribution of C 1 –C 3 alkyl nitrates have been investigated using a global three-dimensional chemistry transport model, STOCHEM-CRI. Alkyl nitrates (RONO 2 ) are significant NO x reservoir species and the more detailed VOC oxidation mechanism (CRI v2-R5) leads to greater photochemical production. RONO 2 are significant sources of NO x in regions remote from NO x sources. The study shows that the global burden and the atmospheric life-time of C 1 –C 3 alkyl nitrates are 113 Gg and 9–10 days, respectively, which are in excellent agreement with estimates established by previous studies. The abundance of alkyl nitrates have been found to be higher in the continental atmosphere, with CH 3 ONO 2 mixing ratios up to 20 ppt over the Amazon rainforest. Up to 15, 10, 2, and 5 ppt of modelled CH 3 ONO 2 , C 2 H 5 ONO 2 , n-C 3 H 7 ONO 2 and i-C 3 H 7 ONO 2 have been found in the northern hemisphere over regions with large anthropogenic emissions of NO x and VOCs. The combination of atmospheric production and long-range transport led to high alkyl nitrate levels at high latitudes. The model performance for C 1 –C 3 alkyl nitrates was established using observations from nine flights and nine field campaigns. The comparison shows a tendency towards model under-prediction of the observations, particularly in the southern hemispheric marine boundary layer, possibly due to the absence of oceanic production mechanisms and air-sea exchange processes in the model. The discrepancies between model and observed seasonal cycles, especially of CH 3 ONO 2 , in both hemispheres are discussed.

Simulated stratospheric temperatures over the period 1979–2016 in models from the Chemistry-Climate Model Initiative are compared with recently updated and extended satellite data sets. The multimodel mean global temperature trends over 1979–2005 are -0.88 ± 0.23, -0.70 ± 0.16, and -0.50 ± 0.12 K/decade for the Stratospheric Sounding Unit (SSU) channels 3 (~40–50 km), 2 (~35–45 km), and 1 (~25–35 km), respectively (with 95% confidence intervals). These are within the uncertainty bounds of the observed temperature trends from two reprocessed SSU data sets. In the lower stratosphere, the multimodel mean trend in global temperature for the Microwave Sounding Unit channel 4 (~13–22 km) is -0.25 ± 0.12 K/decade over 1979–2005, consistent with observed estimates from three versions of this satellite record. The models and an extended satellite data set comprised of SSU with the Advanced Microwave Sounding Unit-A show weaker global stratospheric cooling over 1998–2016 compared to the period of intensive ozone depletion (1979–1997). This is due to the reduction in ozone-induced cooling from the slowdown of ozone trends and the onset of ozone recovery since the late 1990s. In summary, the results show much better consistency between simulated and satellite-observed stratospheric temperature trends than was reported by Thompson et al. (2012, https://doi.org/10.1038/nature11579) for the previous versions of the SSU record and chemistry-climate models. The improved agreement mainly comes from updates to the satellite records; the range of stratospheric temperature trends over 1979–2005 simulated in Chemistry-Climate Model Initiative models is comparable to the previous generation of chemistry-climate models.

Emissions from anthropogenic activity are known to have deleterious impacts on human and ecosystem health and as such a significant amount of time, effort and money has been spent developing legislation to minimise their effects. Here we use a state of the art coupled chemistry-climate model HadGEM2-ES, with extended tropospheric chemistry, to assess the impacts that changes in emissions from anthropogenic activity have had on the burden and impacts of air pollutants over the last three decades. We use HadGEM2-ES to assess an alternative trajectory in air pollutant emissions to that which we have seen, with a regional focus on the contiguous United States and areas of Western Europe. This alternative trajectory can be considered to reflect a world avoided. In this world avoided, the significant levels of air pollution legislation imposed over the last three decades are simulated to not have come into effect in the contiguous United States and Western Europe. Rather a business as usual emission scenario is followed from 1970 to the present day. By combining the results of simulations of the world avoided with a base case present day atmosphere our model runs demonstrate that as a result of air pollution legislation, over 500 000 early mortalities a year have been mitigated owing to extensive reduction in sulfate aerosol and up to 8000 early mortalities a year have been mitigated as a result of improvements in ozone and nitrogen dioxide pollution. These results highlight the important role of legislation in reducing air pollution related mortality in these areas of the globe and highlight a compelling case for developing regions to follow.

The Montreal Protocol has succeeded in limiting major ozone-depleting substance emissions, and consequently stratospheric ozone concentrations are expected to recover this century. However, there is a large uncertainty in the rate of regional ozone recovery in the Northern Hemisphere. Here we identify a Eurasia-North America dipole mode in the total column ozone over the Northern Hemisphere, showing negative and positive total column ozone anomaly centres over Eurasia and North America, respectively. The positive trend of this mode explains an enhanced total column ozone decline over the Eurasian continent in the past three decades, which is closely related to the polar vortex shift towards Eurasia. Multiple chemistry-climate-model simulations indicate that the positive Eurasia-North America dipole trend in late winter is likely to continue in the near future. Our findings suggest that the anticipated ozone recovery in late winter will be sensitive not only to the ozone-depleting substance decline but also to the polar vortex changes, and could be substantially delayed in some regions of the Northern Hemisphere extratropics., Climate change can exert a significant effect on the ozone recovery. Here, the authors show that the Arctic polar vortex shift associated with Arctic sea-ice loss could slow down ozone recovery over the Eurasian continent.

We have derived values of the Ultraviolet Index (UVI) at solar noon using the Tropospheric Ultraviolet Model (TUV) driven by ozone, temperature and aerosol fields from climate simulations of the first phase of the Chemistry-Climate Model Initiative (CCMI-1). Since clouds remain one of the largest uncertainties in climate projections, we simulated only the clear-sky UVI. We compared the modelled UVI climatologies against present-day climatological values of UVI derived from both satellite data (the OMI-Aura OMUVBd product) and ground-based measurements (from the NDACC network). Depending on the region, relative differences between the UVI obtained from CCMI/TUV calculations and the ground-based measurements ranged between −5.9% and 10.6%. We then calculated the UVI evolution throughout the 21st century for the four Representative Concentration Pathways (RCPs 2.6, 4.5, 6.0 and 8.5). Compared to 1960s values, we found an average increase in the UVI in 2100 (of 2–4%) in the tropical belt (30°N-30°S). For the mid-latitudes, we observed a 1.8 to 3.4 % increase in the Southern Hemisphere for RCP 2.6, 4.5 and 6.0, and found a 2.3% decrease in RCP 8.5. Higher increases in UVI are projected in the Northern Hemisphere except for RCP 8.5. At high latitudes, ozone recovery is well identified and induces a complete return of mean UVI levels to 1960 values for RCP 8.5 in the Southern Hemisphere. In the Northern Hemisphere, UVI levels in 2100 are higher by 0.5 to 5.5% for RCP 2.6, 4.5 and 6.0 and they are lower by 7.9% for RCP 8.5. We analysed the impacts of greenhouse gases (GHGs) and ozone-depleting substances (ODSs) on UVI from 1960 by comparing CCMI sensitivity simulations (1960–2100) with fixed GHGs or ODSs at their respective 1960 levels. As expected with ODS fixed at their 1960 levels, there is no large decrease in ozone levels and consequently no sudden increase in UVI levels. With fixed GHG, we observed a delayed return of ozone to 1960 values, with a corresponding pattern of change observed on UVI, and looking at the UVI difference between 2090s values and 1960s values, we found an 8 % increase in the tropical belt during the summer of each hemisphere. Finally we show that, while in the Southern Hemisphere the UVI is mainly driven by total ozone column, in the Northern Hemisphere both total ozone column and aerosol optical depth drive UVI levels, with aerosol optical depth having twice as much influence on the UVI as total ozone column does.

Isoprene is a~precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO2 levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry–climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work, we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the Master Chemical Mechanism) over a range of NOx and isoprene emissions, through the use of O3 isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NOx reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene-rich regions, the response of the schemes varies considerably. The wide-ranging response is due to differences in the model descriptions of the peroxy radical chemistry, particularly their relative rates of reaction towards NO, leading to ozone formation, or HO2, leading to termination. Also important is the yield of isoprene nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NOx reservoir species, tend to produce more ozone locally and less away from the source region. We also note changes in other key oxidants such as NO3 and OH (due to the inclusion of additional isoprene-derived HOx recycling pathways). These have implications for secondary organic aerosol formation, as does the inclusion of an epoxide formation pathway in one of the mechanisms. By combining the emissions and O3 data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements and laboratory studies are needed to validate these reduced mechanisms especially under high-volatile-organic-compound, low-NOx conditions.

All recent climatic projections for the next century suggest that we are heading towards a warmer climate than today (Intergovernmental Panel on Climate Change; Fifth Assessment Report), driven by increasing atmospheric burdens of anthropogenic greenhouse gases. In particular, the volume mixing ratio of methane, the second-most important anthropogenic greenhouse gas, has increased by a factor of ∼2.5 from the beginning of the European Industrial Revolution. Due to their complex responses to climatic factors, understanding of the dynamics of future global methane emissions and sinks is crucial for the next generation of climate projections. Of relevance to this problem, the Earth likely experienced warmer average temperatures than today during the Last Interglacial (LIG) period (130–115 kaBP). Interestingly, ice cores do not indicate a different methane mixing ratio from the Pre-Industrial Holocene (PIH), in other words the current interglacial period prior to anthropogenic influence. This is surprising as warmer temperatures might be expected to increase methane emissions. The present study aims to improve our understanding of the changes in the global methane budget through quantifying the relative importance of sources and sinks of methane during the last full glacial–interglacial cycle. A fairly limited number of studies have investigated this cycle at the millenium time scale with most of them examining the doubling in CH 4 from the Last Glacial Maximum (LGM) to the PIH. Though it is still a matter of debate, a general consensus suggests a predominant role to the change in methane emissions from wetlands and only a limited change in the oxidising capacity of the atmosphere. In the present study we provide an estimate of the relative importance of sources and sinks during the LIG period, using a complex climate–chemistry model to quantify the sinks, and a methane emissions model included in a global land surface model, for the sources. We are not aware of any previous studies that have explicitly tackled sources and sinks of methane in the previous interglacial. Our results suggest that both emissions and sinks of methane were higher during the LIG period, relative to the PIH, resulting in similar atmospheric concentrations of methane. Our simulated change in methane lifetime is primarily driven by climate (i.e. air temperature and humidity). However, a significant part of the reduced methane lifetime is also attributable to the impact of changes in NO x emissions from lightning. An increase in biogenic emissions of non-methane volatile organic compounds during the LIG seems unlikely to have compensated for the impact of temperature and humidity. Surface methane emissions from wetlands were higher in northern latitudes due to an increase of summer temperature, whilst the change in the tropics is less certain. Simulated methane emissions are strongly sensitive to the atmospheric forcing, with most of this sensitivity related to changes in wetland extent.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

A global 3-D chemistry and transport model, STOCHEM integrated with a detailed VOC oxidation scheme (CRI v2-R5) has been employed to study the important NOx reservoir compound, peroxyacetyl nitrate (PAN). Globally, PAN is produced entirely by the reaction of acetyl peroxy radicals (CH3CO3)with NO2 and up to 2.0 ppb of PAN is found over the polluted regions of North America during June-July-August for the present scenario. The imbalances between model and measurement data are noted, with STOCHEM-CRI overestimating PAN mixing ratios relative to the measurement data by +17 and+80 pptv for the lower and upper troposphere, respectively. The inclusion of additional HOx recycling mechanisms (e.g. related to isoprene oxidation) in STOCHEM-CRI causes a decrease in PAN in a present scenario by as much as 40% over sink regions and reduces the model-measurement disagreement by 90% for the lower troposphere and 40% for the upper troposphere. The lower NOx emissions and CH3CO3 formation upon including HOx recycling in a preindustrial scenario led to a decrease in PAN formation by as much as 40%. The decrease in PAN formation results in less nitrogen being transported to remote regions which in turn leads to the greatest percentage change in O3 concentration (9% decrease) in the equatorial regions.

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.

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.

We have diagnosed the lifetimes of long-lived source gases emitted at the surface and removed in the stratosphere using six three-dimensional chemistry-climate models and a two-dimensional model. The models all used the same standard photochemical data. We investigate the effect of different definitions of lifetimes, including running the models with both mixing ratio (MBC) and flux (FBC) boundary conditions. Within the same model, the lifetimes diagnosed by different methods agree very well. Using FBCs versus MBCs leads to a different tracer burden as the implied lifetime contained in the MBC value does not necessarily match a model's own calculated lifetime. In general, there are much larger differences in the lifetimes calculated by different models, the main causes of which are variations in the modeled rates of ascent and horizontal mixing in the tropical midlower stratosphere. The model runs have been used to compute instantaneous and steady state lifetimes. For chlorofluorocarbons (CFCs) their atmospheric distribution was far from steady state in their growth phase through to the 1980s, and the diagnosed instantaneous lifetime is accordingly much longer. Following the cessation of emissions, the resulting decay of CFCs is much closer to steady state. For 2100 conditions the model circulation speeds generally increase, but a thicker ozone layer due to recovery and climate change reduces photolysis rates. These effects compensate so the net impact on modeled lifetimes is small. For future assessments of stratospheric ozone, use of FBCs would allow a consistent balance between rate of CFC removal and model circulation rate.

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.

In this study, we use a high resolution version of the Cambridge p-TOMCAT model, along with data collected during the 2008 NERC-funded Oxidant and Particle Photochemical Processes (OP3) project, to examine the potential impact of the expansion of oil palm in Borneo on air quality and atmospheric composition. Several model emission scenarios are run for the OP3 measurement period, incorporating emissions from both global datasets and local flux measurements. Isoprene fluxes observed at a forest site during OP3 were considerably less than fluxes calculated using the MEGAN model. Incorporating the observed isoprene fluxes into p-TOMCAT substantially improved the comparison between modelled and observed isoprene surface mixing ratios and OH concentrations relative to using the MEGAN emissions. If both observed isoprene fluxes and HOx recycling chemistry were included, the ability of the model to capture diurnal variations in isoprene and OH was further improved. However, a similar improvement was also achieved using a~standard chemical mechanism without HOx recycling, by fixing boundary layer isoprene concentrations over Borneo to follow the OP3 observations. Further model simulations, considering an extreme scenario with all of Borneo converted to oil palm plantation, were run to determine the maximum atmospheric impact of land use change in Borneo. In these simulations, the level of nitrogen oxides was found to be critical. If only isoprene emissions from oil palm are considered, then large scale conversion to oil palm produced a decrease in monthly mean surface ozone of up to ~20%. However, if related changes in NOx emissions from fertilisation, industrial processing and transport are also included then ozone increases of up to ~70% were calculated. Although the largest changes occurred locally, the model also calculated significant regional changes of O3, OH and other species downwind of Borneo and in the free troposphere.

Atmospheric chemistry is driven by photolytic reactions, making their modelling a crucial component of atmospheric models. We describe the implementation and validation of Fast-JX, a state of the art model of interactive photolysis, into the MetUM chemistry-climate model. This allows for interactive photolysis rates to be calculated in the troposphere and augments the calculation of the rates in the stratosphere by accounting for clouds and aerosols in addition to ozone. In order to demonstrate the effectiveness of this new photolysis scheme we employ new methods of validating the model, including techniques for sampling the model to compare to flight track and satellite data.

We present surface layer measurements made over Hudson Bay sea ice during February/March 2008 from the COBRA (Impact of combined iodine and bromine release on the Arctic atmosphere) experiment which formed part of the International OASIS (Ocean-Atmosphere-Sea Ice-Snowpack) IPY programme. All components of the local surface energy balance were measured and it was defined by net radiative cooling throughout most of the day, mainly balanced by the conductive heat flux from the warmer sea water to the cooler sea ice at the surface, and a small net radiative warming for a few hours after midday. Unique ground-level ozone fluxes were measured by eddy covariance and deposition velocities ranged from +0.5 mm s(-1) (deposition) to -1.5 mm s(-1) (emission). Ozone profile measurements suggested ozone flux divergence within the surface layer. The observed bi-directional fluxes and flux divergence with height reveal the complexity of surface ozone fluxes in the Arctic spring time surface layer, and show that ozone exchange with the sea ice surface is best probed using the eddy covariance method alongside frequent or continuous profile measurements. In this study, the local in-situ ozone-halogen photochemistry was identified as weakly controlling the measured ozone flux, whereas horizontal advection and vertical mixing were considered more important in influencing fluxes. Under these conditions, several measurement sites would be desirable in order to quantify the contribution of advection to the local surface exchange. (C) 2011 Elsevier Ltd. All rights reserved.

We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NO x emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.

The rate coefficient for the reaction HO2 + NO2 has been measured using a turbulent flow technique with high pressure chemical ionization mass spectrometry for the detection of reactants. The rate constant was measured between 75 and 700 Torr and at 298, 223 and 200 K. This work represents the first experimental evaluation of this rate coefficient at temperatures below 219 K. The kinetic data has been evaluated in both a global 3-dimensional atmospheric chemistry model of the troposphere and in a steady-state model. These new data improve the agreement between the steady-state model and field measurements but an unresolved discrepancy remains. Field measurements suggest that some pernitric acid may persist in the upper troposphere and if this background is taken into consideration together with these new kinetic data, good agreement between steady-state models and measurements emerge. Global model runs show that on average HO2NO2 levels are reduced by 30–40% in the upper troposphere and 20–30% in the free troposphere. This reduction in HO2NO2 leads to increases in HOx and NOx in the upper troposphere, most notably a rise of 1–12% in OH and around 5% in NOx.

A secondary organic aerosol (SOA) code, coupled to the reduced Common Representative Intermediates chemical mechanism (CRI v2-R5), has been used in the global 3-D chemistry-transport model, STOCHEM, to simulate the global distribution of organic aerosol (OA) mass loadings. The SOA code represents the gas-to-aerosol partitioning of products formed over several generations of oxidation of a variety of organic precursors emitted from anthropogenic, biogenic and biomass burning sources. The model also includes emissions of primary organic aerosol (POA), based on the AeroCom inventory and the Global Fire Emissions database (GFED). The calculated burdens for POA, 0.89 Tg, and SOA, 0.23 Tg, are well within the range of values that have been reported in previous modelling studies. The calculated SOA annual in-situ production of 22.5 Tg yr −1 also falls within the 8–110 Tg yr −1 range calculated by other models, but is somewhat lower than observationally-constrained top-down estimates which have been reported recently. The oxidation of biogenic precursors is found to account for about 90% of the global SOA burden, and this makes a substantial contribution to the highest annual mean surface OA concentrations (up to 8 μg m −3 ), which are simulated in tropical forested regions. Comparison of the simulated OA mass loadings with surface observations from a variety of locations indicate a good description of the OA distribution, but with an average underestimation of about a factor of 3. Sustained formation of SOA into the free troposphere is simulated, with important contributions from second and third-generation products of terpene oxidation in the upper troposphere. Comparison of the simulated OA mass loadings with vertical profiles from the ACE-Asia campaign indicates a very good description of the relative variation of OA with altitude, but with consistent underestimation of about a factor of 5. Although the absolute magnitude of the global source strength is underestimated, this consistency nonetheless provides support for an important role for multigenerational oxidation chemistry as a large source of SOA in the free troposphere, and lends credence to the necessity of representing condensable material formed over several generations of VOC oxidation in global chemistry-transport models.

The chemical mechanisms describing the photo-oxidation of isoprene in current Chemistry Transport Models (CTMs) have been intercompared in a series of box model experiments. The mechanisms ranged in size and complexity from ∼600 reactions to ∼25 reactions. The box model experiments covered two isoprene emission strengths over a broad range of NO emissions to assess the performances of the mechanisms over the spectrum of atmospherically relevant conditions. There was some variability in the simulated oxidation rates of isoprene and formation rates of ozone. The variability in performance is a consequence of the details of the underlying chemistry as represented in the mechanisms, and of the different assumptions and approximations made in mechanism reduction. These differences are illustrated and discussed for a series of species involved in the degradation of isoprene and the ozone formation mechanism, namely: HOx radicals; organic peroxy radicals (RO2); hydroperoxides; oxidised organic nitrogen compounds; and major carbonyl products. The results also confirm that all the considered isoprene mechanisms are unable to generate/recycle HOx at the rates needed to match recently reported observations at locations characterized by low levels of NOx.

A box model simulating tropospheric conditions was used to trace the oxidation pathways of 17 volatile organic compounds (VOCs) covering saturated, olefinic, oxygenated and aromatic species. Yields of carbon monoxide (CO), carbon dioxide (CO 2 ) and other oxidation products were calculated over the duration of the model simulation. Conversion factors to CO and CO 2 were determined for individual VOCs at various simulated levels of NO x (an indicator of pollution level). Global budget estimates for CO and CO 2 formed from the oxidation of reduced carbon were then calculated based on these conversion factors. At medium levels of NO x (160 pptv) we calculate that isoprene degradation forms 626 ± 250 Tg CO yr −1 , whilst the oxidation of non-methane VOCs produces 955 ± 362 Tg CO yr −1 and VOC oxidation accounts for 1804 ± 660 Tg CO yr −1 , all higher than previous literature estimates. To maintain the oxidation balance within global chemical transport models which do not include a detailed suite of non-methane VOCs (NMVOCs) it may be vital to include this CO source from NMVOC oxidation. We found the oxidation of NMVOCs to produce 545 ± 211 Tg C yr −1 as CO 2 , whilst overall VOC oxidation accounted for 916 ± 338 Tg C yr −1 of CO 2 , at medium NO x .

A box model simulating tropospheric conditions was used to trace the oxidation pathways of 15 volatile organic compounds (VOCs). Yields of hydrogen were calculated over the duration of the model simulation and conversion factors to hydrogen were determined for individual VOCs at various simulated levels of NOx. These were used to produce global budget estimates. Oxidation of non-methane VOCs (NMVOCs) formed 20.1 Tg H2/year, while the overall VOC oxidation accounted for 45.3 Tg H2/year. To maintain the oxidation balance within global chemical transport models which do not include a detailed suite of NMVOC it may be vital to include this hydrogen source from NMVOC oxidation. Copyright  2010 Royal Meteorological Society

Recently reported model-measurement discrepancies for the concentrations of the HOx radical species (OH and HO2) in locations characterized by high emission rates of isoprene have indicated possible deficiencies in the representation of OH recycling and formation in isoprene mechanisms currently employed in numerical models; particularly at low levels of NOx. Using version 3.1 of the Master Chemical Mechanism (MCM v3.1) as a base mechanism, the sensitivity of the system to a number of detailed mechanistic changes is examined for a wide range of NOx levels, using a simple box model. The studies consider sensitivity tests in relation to three general areas for which experimental and/or theoretical evidence has been reported in the peer-reviewed literature, as follows: (1) implementation of propagating channels for the reactions of HO2 with acyl and β-oxo peroxy radicals with HO2, with support from a number of studies; (2) implementation of the OH-catalysed conversion of isoprene-derived hydroperoxides to isomeric epoxydiols, as characterised by Paulot et al.~(2009a); and (3) implementation of a mechanism involving respective 1,5 and 1,6 H atom shift isomerisation reactions of the β-hydroxyalkenyl and cis-δ-hydroxyalkenyl peroxy radical isomers, formed from the sequential addition of OH and O2 to isoprene, based on the theoretical study of Peeters et al. (2009). All the considered mechanistic changes lead to simulated increases in the concentrations of OH, with (1) and (2) resulting in respective increases of up to about 7% and 16%, depending on the level of NOx. (3) is found to have potentially much greater impacts, with enhancements in OH concentrations of up to a factor of about 3.3, depending on the level of NOx, provided the (crucial) rapid photolysis of the hydroperoxy-methyl-butenal products of the cis-δ-hydroxyalkenyl peroxy radical isomerisation reactions is represented, as also postulated by Peeters et al.~(2009). Additional tests suggest that the mechanism with the reported parameters cannot be fully reconciled with atmospheric observations and existing laboratory data without some degree of parameter refinement and optimisation which would probably include a reduction in the peroxy radical isomerisation rates and a consequent reduction in the OH enhancement propensity. However, an order of magntitude reduction in the isomerisation rates is still found to yield notable enhancements in OH concentrations of up to a factor of about 2, with the maximum impact at the low end of the considered NOx range. A parameterized representation of the mechanistic changes is optimized and implemented into a reduced variant of the Common Representative Intermediates mechanism (CRI v2-R5), for use in the STOCHEM global chemistry-transport model. The impacts of the modified chemistry in the global model are shown to be consistent with those observed in the box model sensitivity studies, and the results are illustrated and discussed with a particular focus on the tropical forested regions of the Amazon and Borneo where unexpectedly elevated concentrations of OH have recently been reported.

In the 1990s the rates of increase of greenhouse gas concentrations, most notably of methane, were observed to change, for reasons that have yet to be fully determined. This period included the eruption of Mt. Pinatubo and an El Niño warm event, both of which affect biogeochemical processes, by changes in temperature, precipitation and radiation. We examine the impact of these changes in climate on global isoprene emissions and the effect these climate dependent emissions have on the hydroxy radical, OH, the dominant sink for methane. We model a reduction of isoprene emissions in the early 1990s, with a maximum decrease of 40 Tg(C)/yr in late 1992 and early 1993, a change of 9%. This reduction is caused by the cooler, drier conditions following the eruption of Mt. Pinatubo. Isoprene emissions are reduced both directly, by changes in temperature and a soil moisture dependent suppression factor, and indirectly, through reductions in the total biomass. The reduction in isoprene emissions causes increases of tropospheric OH which lead to an increased sink for methane of up to 5 Tg(CH4)/year, comparable to estimated source changes over the time period studied. There remain many uncertainties in the emission and oxidation of isoprene which may affect the exact size of this effect, but its magnitude is large enough that it should remain important.

A reduced chemical scheme (CRIv2-R5) which describes ozone formation from the tropospheric degradation of methane and 22 emitted non-methane hydrocarbons and oxygenated volatile organic compounds has been applied in a global-3D chemistry transport model (STOCHEM). The scheme, which contains 220 species in 609 reactions, has been used to simulate ozone and its precursors for the meteorological year of 1998 and the results have been compared with those from STOCHEM runs with its original chemistry. Compared with the original chemistry scheme, the degradation of a larger number of more reactive VOCs in the CRI scheme results in the formation (and their consequent transportation) of more NOx active reservoirs thus leading to formation of more ozone away from land-based sources. Conversely, the more reactive VOCs also lead to greater removal of OH in continental areas and greater formation of OH in marine environments. STOCHEM run with the CRI scheme simulates more ozone (by up to 10 ppb), which results in better agreement with observed vertical ozone profiles. The CRI scheme transforms the globally and annually integrated ozone budget for the considered year in STOCHEM from a net loss of −55 Tg yr−1 to a net gain of +50 Tg yr−1.

A new model, BAMBO (Bristol’s Atmospheric Marine Boundary layer mOdel), was developed in order to investigate the reaction between peroxy radicals (RO2 )a nd the hydroxyl radical (OH) under typical marine boundary layer (MBL) conditions. The results of this work have shown that the inclusion of the title reaction has negligible effects on inorganic species and ozone but can have significant effects on predicted atmospheric mixing ratios of oxygenated volatile organic compounds (OVOCs), which are generally poorly represented in atmospheric models. This work highlights that the title reaction may be important to modelling trace gas composition in the MBL. However, thorough experimental and theoretical studies are needed to clarify many of the assumptions made. Copyright  2009 Royal Meteorological Society