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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

Here we present high frequency long-term observations of ethane, benzene and methyl chloride from the AGAGE Ragged Point, Barbados, monitoring station made using a custom built GC-MS system. Our analysis focuses on the first three years of data (2005–2007) and on the interpretation of periodic episodes of high concentrations of these compounds. We focus specifically on an exemplar episode during September 2007 to assess if these measurements are impacted by long-range transport of biomass burning and biogenic emissions. We use the Lagrangian Particle Dispersion model, NAME, run forwards and backwards in time to identify transport of air masses from the North East of Brazil during these events. To assess whether biomass burning was the cause we used hot spots detected using the MODIS instrument to act as point sources for simulating the release of biomass burning plumes. Excellent agreement for the arrival time of the simulated biomass burning plumes and the observations of enhancements in the trace gases indicates that biomass burning strongly influenced these measurements. These modelling data were then used to determine the emissions required to match the observations and compared with bottom up estimates based on burnt area and literature emission factors. Good agreement was found between the two techniques highlight the important role of biomass burning. The modelling constrained by in situ observations suggests that the emission factors were representative of their known upper limits, with the in situ data suggesting slightly greater emissions of ethane than the literature emission factors account for. Further analysis was performed concluding only a small role for biogenic emissions of methyl chloride from South America impacting measurements at Ragged Point. These results highlight the importance of long-term high frequency measurements of NMHC and ODS and highlight how these data can be used to determine sources of emissions 1000’s km away.

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.

Earth system models (ESMs) are increasing in complexity by incorporating more processes than their predecessors, making them potentially important tools for studying the evolution of climate and associated biogeochemical cycles. However, their coupled behaviour has only recently been examined in any detail, and has yielded a very wide range of outcomes. For example, coupled climate–carbon cycle models that represent land-use change simulate total land carbon stores at 2100 that vary by as much as 600 Pg C, given the same emissions scenario. This large uncertainty is associated with differences in how key processes are simulated in different models, and illustrates the necessity of determining which models are most realistic using rigorous methods of model evaluation. Here we assess the state-of-the-art in evaluation of ESMs, with a particular emphasis on the simulation of the carbon cycle and associated biospheric processes. We examine some of the new advances and remaining uncertainties relating to (i) modern and palaeodata and (ii) metrics for evaluation. We note that the practice of averaging results from many models is unreliable and no substitute for proper evaluation of individual models. We discuss a range of strategies, such as the inclusion of pre-calibration, combined process- and system-level evaluation, and the use of emergent constraints, that can contribute to the development of more robust evaluation schemes. An increasingly data-rich environment offers more opportunities for model evaluation, but also presents a challenge. Improved knowledge of data uncertainties is still necessary to move the field of ESM evaluation away from a "beauty contest" towards the development of useful constraints on model outcomes.

We examine the effects of ozone precursor emissions from megacities on present-day air quality using the global chemistry–climate model UM-UKCA (UK Met Office Unified Model coupled to the UK Chemistry and Aerosols model). The sensitivity of megacity and regional ozone to local emissions, both from within the megacity and from surrounding regions, is important for determining air quality across many scales, which in turn is key for reducing human exposure to high levels of pollutants. We use two methods, perturbation and tagging, to quantify the impact of megacity emissions on global ozone. We also completely redistribute the anthropogenic emissions from megacities, to compare changes in local air quality going from centralised, densely populated megacities to decentralised, lower density urban areas. Focus is placed not only on how changes to megacity emissions affect regional and global NOx and O3, but also on changes to NOy deposition and to local chemical environments which are perturbed by the emission changes. The perturbation and tagging methods show broadly similar megacity impacts on total ozone, with the perturbation method underestimating the contribution partially because it perturbs the background chemical environment. The total redistribution of megacity emissions locally shifts the chemical environment towards more NOx-limited conditions in the megacities, which is more conducive to ozone production, and monthly mean surface ozone is found to increase up to 30% in megacities, depending on latitude and season. However, the displacement of emissions has little effect on the global annual ozone burden (0.12% change). Globally, megacity emissions are shown to contribute ~3% of total NOy deposition. The changes in O3, NOx and NOy deposition described here are useful for quantifying megacity impacts and for understanding the sensitivity of megacity regions to local emissions. The small global effects of the 100% redistribution carried out in this study suggest that the distribution of emissions on the local scale is unlikely to have large implications for chemistry–climate processes on the global scale.

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, suggesting a slightly longer-lasting/stronger stratospheric descent in runs with higher ozone destruction. We contrast the idealised model behaviour with interannual variability in ozone and N2O as observed by the MIPAS instrument on ENVISAT, highlighting the similarity of the modelled climate equilibrium changes to the year 2006/2007 in observations. We conclude that the climate system can respond quite sensitively to small chemical perturbations, that circulation adjustments seen in the model can occur in reality, and that coupled chemistry-climate models are needed for an assessment of future ozone and climate changes.

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.

Ozone (O3) from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) has been used to calculate tropospheric ozone radiative forcings (RFs). All models applied a common set of anthropogenic emissions, which are better constrained for the present-day than the past. Future anthropogenic emissions follow the four Representative Concentration Pathway (RCP) scenarios, which define a relatively narrow range of possible air pollution emissions. We calculate a value for the pre-industrial (1750) to present-day (2010) tropospheric ozone RF of 410 mW m−2. The model range of pre-industrial to present-day changes in O3 produces a spread (±1 standard deviation) in RFs of ±17%. Three different radiation schemes were used – we find differences in RFs between schemes (for the same ozone fields) of ±10%. Applying two different tropopause definitions gives differences in RFs of ±3%. Given additional (unquantified) uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of ±30% for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (44±12%), nitrogen oxides (31 ± 9%), carbon monoxide (15 ± 3%) and non-methane volatile organic compounds (9 ± 2%); earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 42 mW m−2 DU−1, a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (mW m−2; relative to 1750) for the four future scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5) of 350, 420, 370 and 460 (in 2030), and 200, 300, 280 and 600 (in 2100). Models show some coherent responses of ozone to climate change: decreases in the tropical lower troposphere, associated with increases in water vapour; and increases in the sub-tropical to mid-latitude upper troposphere, associated with increases in lightning and stratosphere-to-troposphere transport. Climate change has relatively small impacts on global mean tropospheric ozone RF.

Present day tropospheric ozone and its changes between 1850 and 2100 are considered, analysing 15 global models that participated in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The ensemble mean compares well against present day observations. The seasonal cycle correlates well, except for some locations in the tropical upper troposphere. Most (75 %) of the models are encompassed with a range of global mean tropospheric ozone column estimates from satellite data, but there is a suggestion of a high bias in the Northern Hemisphere and a low bias in the Southern Hemisphere, which could indicate deficiencies with the ozone precursor emissions. Compared to the present day ensemble mean tropospheric ozone burden of 337 ± 23 Tg, the ensemble mean burden for 1850 time slice is ~30% lower. Future changes were modelled using emissions and climate projections from four Representative Concentration Pathways (RCPs). Compared to 2000, the relative changes in the ensemble mean tropospheric ozone burden in 2030 (2100) for the different RCPs are: −4% (−16%) for RCP2.6, 2% (−7%) for RCP4.5, 1% (−9%) for RCP6.0, and 7% (18%) for RCP8.5. Model agreement on the magnitude of the change is greatest for larger changes. Reductions in most precursor emissions are common across the RCPs and drive ozone decreases in all but RCP8.5, where doubled methane and a 40–150% greater stratospheric influx (estimated from a subset of models) increase ozone. While models with a high ozone burden for the present day also have high ozone burdens for the other time slices, no model consistently predicts large or small ozone changes; i.e. the magnitudes of the burdens and burden changes do not appear to be related simply, and the models are sensitive to emissions and climate changes in different ways. Spatial patterns of ozone changes are well correlated across most models, but are notably different for models without time evolving stratospheric ozone concentrations. A unified approach to ozone budget specifications and a rigorous investigation of the factors that drive tropospheric ozone is recommended to help future studies attribute ozone changes and inter-model differences more clearly.

4 pags, 3 figs, 1 tab, [1] Simulations with a chemistry-climate model (CCM) show a future increase in the stratospheric source gas injection (SGI) of biogenic very short-lived substances (VSLS). For 2000, the modelled SGI of bromine from VSLS is ∼1.7 parts per trillion (pptv) and largest over the tropical West Pacific. For 2100, this increases to ∼2.0 and ∼2.7 pptv when the model is forced with Intergovernmental Panel on Climate Change (IPCC) representative concentration pathways (RCPs) 4.5 and 8.5. The increase is largely due to stronger tropical deep convection transporting more CHBr3 to the lower stratosphere. For CH2Br2, CHBr2Cl, CH2BrCl and CHBrCl2, changes to primary oxidant OH determines their SGI contribution. Under RCP 4.5 (moderate warming), OH increases in a warmer, more humid troposphere. Under RCP 8.5 (extreme warming) OH decreases significantly due to a large methane increase, allowing greater SGI of bromine from these VSLS. Potentially enhanced VSLS emissions in the future would further increase these estimates. © 2012. American Geophysical Union. All Rights Reserved., This work was supported by the UK NERC and the EU SHIVA project (SHIVA-226224-FP7-ENV-2008-1). We also thank Mohit Dalvi (Met Office) and NCAS-CMS for UM support.

We know from the ice record that the concentration of atmospheric methane, [CH4], at the Last Glacial Maximum (LGM) was roughly half that in the pre-industrial era (PI), buthow much of the difference was source-driven, and how much was sink-driven, remains uncertain. Recent developments include: a higher estimate of the LGM-PI change in methane emissions from wetlands―the dominant, natural methane source; and the possible recycling of OH consumed in isoprene oxidation―the principal methane sink. Here, in view of these developments, we use an atmospheric chemistry-transport model to re-examine the main factors affecting OH during this period: changes in air temperature and emissions of non-methane volatile organic compounds from vegetation. We find that their net effect was negligible(with and without an OH recycling mechanism), implyingthe change in [CH4] was almost entirely source driven―a conclusion that, though subject to significant uncertainties,can be reconciled with recent methane source estimates.

Gas-phase ethene ozonolysis experiments were conducted at room temperature to determine formic acid yields as a function of relative humidity (RH) using the integrated EXTreme RAnge chamber-Chemical Ionisation Mass Spectrometry technique, employing a CH3I ionisation scheme. RHs studied were 2OO with water compared with decomposition. This analysis suggests that the rate of reaction with water ranges between 1×10−12–1×10−15 cm3 molecule−1 s−1 and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Global model integrations suggest that this reaction between CH2OO and water may dominate the production of HC(O)OH in the atmosphere.

[1] A global chemistry-climate model is used to assess the impact on atmospheric composition of the regeneration and recycling of HOx in the photo-oxidation of isoprene. The impact is explored subject to present-day, pre-industrial and future climate/emission scenarios. Our calculations show that, in all cases, the inclusion of uni-molecular isomerisations of the isoprene hydroxy-peroxy radicals leads to enhanced production of HOx radicals and ozone. The global burden of ozone increases by 25–36 Tg (8–18%), depending on the climate/emissions scenario, whilst the changes in OH lead to decreases in the methane lifetime of between 11% in the future and 35% in the pre-industrial. Critically the size of the change in methane lifetime depends on the VOC/NOx emission ratio. The results of the present-day calculations suggest a certain amount of parameter refinement is still needed to reconcile the updated chemistry with field observations (particularly for HO2+RO2). However, the updated chemistry could have far-reaching implications for: future-climate predictions; projections of future oxidising capacity; and our understanding of past changes in oxidising capacity.

Heteroatomic unsaturated volatile organic compounds (HUVOCs) are common trace components of the atmosphere, yet their diverse chemical behaviour presents difficulties for predicting their oxidation kinetics using structure-activity relationships (SARs). An existing SAR is adapted to help meet this challenge, enabling the prediction of ozonolysis rates with unprecedented accuracy. The new SAR index, x(H), correlates strongly with available literature measurements of ozonolysis rate coefficients (R(2) = 0.87), a database representing 110 species. It was found that capturing the inductive effect rather than the steric effect is of primary importance in predicting the reactivity of these species, which is to be anticipated since HUVOCs can possess a variety of functional groups with a range of electron-withdrawing and donating tendencies. New experimental measurements of ozonolysis rate coefficients were conducted for 1-penten-3-ol, 3-methyl; ethene, 1,1-dimethoxy; E-2-pentenoic acid; E-1,2-dichloroethene; Z-1,2-dichloroethene; trichloroethene; tetrachloroethene; 1-butene, 3-chloro and 2-chloropropene, and were determined to be 5.15 × 10(-18), 4.82 × 10(-16), 3.07 × 10(-18), 8.05 × 10(-20), 4.88 × 10(-21), 6.04 × 10(-22), 1.56 × 10(-24), 2.26 × 10(-18) and 1.13 × 10(-19) cm(3) molecule(-1) s(-1), respectively. The index of the inductive effect, i(H), is compared with other indices of the electron-withdrawing capacity of a substitution, notably the Taft σ* constants and the rate of reaction of a given species with the hydroxyl radical, both of which are expected to be unaffected by steric factors. i(H) correlates strongly in both cases and suggests a universal response by olefinic species towards electrophilic addition.

A global chemistry transport model is employed to investigate the impact of recent laboratory determinations of photolysis parameters for formaldehyde on concentrations of tropospheric trace gases. Using the new laboratory data, the photolysis of formaldehyde is a more significant removal pathway. HOx levels are increased with the greatest changes towards the top of the troposphere and the poles, making formaldehyde a more significant source of upper tropospheric HOx than previously thought. Global totals of ozone and secondary organic aerosol increase with the rise in ozone being more significant at higher solar zenith angles. Copyright © 2010 Royal Meteorological Society

The configuration of alkyl substituents about carbon-carbon unsaturated bonds exerts a controlling influence on the rate of the ozonolysis reaction. Alkyl substituents can increase (via the inductive effect) and decrease (via the steric effect) the activity of unsaturated bonds, and an accurate description of this information ought to correlate with the ozonolysis rate coefficient. A strong linear relationship is observed (R2 = 0.94), providing the basis of our SAR method. SAR estimates were tested against literature measurements of ozonolysis rate coefficients for 48 aliphatic alkenes and dialkenes, and were found to be accurate to within a factor of 2.3 of the measured value for the entire dataset. This represents a significant improvement over methods reported in the literature, where quoted predictions are at best accurate to within a factor of 6.5. Rates of gas-phase ozonolysis of alkenes and dialkenes can now be predicted with unprecedented accuracy using a simple SAR. The SAR was then validated against new experimental data. Absolute rate coefficients for the gas-phase reaction of ozone with a series of alkenes were determined in a simulation chamber at 295 +/- 2 K and atmospheric pressure by monitoring the loss of ozone in the presence of excess alkene. The rate coefficients (in units of 1 x 10(-18) cm3 molecule(-1) s(-1)) are: 5.12 +/- 0.93 for 1-pentene, 2,3-dimethyl; 406 +/- 49 for 2-pentene, 2-methyl; 151 +/- 5 for (E)-2-hexene, 14.5 +/- 1.0 for 1,5-hexadiene and 20.7 +/- 3.1 for 1,5-hexadiene, 2-methyl. There is good agreement between the experimental and predicted values and the adjustable parameters of the SAR are shown to be insensitive to the inclusion of the new data. The use of the SAR in atmospheric chemical modelling is investigated. Ozonolysis and OH radical rate coefficients are estimated for each alkene and dialkene present in the MCM v3.1. The effects of error within predicted rate coefficients upon modelled concentrations of a number of key species, including O3, OH, HO2, NO and NO2 were rather small and is not in itself a major cause of uncertainty in modelled concentrations.

[1] Following the recent discovery that enols are important intermediates in combustion chemistry, the possible impact of these species on atmospheric chemistry is investigated. A novel mechanism is proposed by which the reactions of enols contribute significantly towards atmospheric carboxylic acid concentrations in the gas-phase. Inclusion of ethenol in the Common Representative Intermediates CRI mechanism was found to increase predicted secondary production of formic acid considerably (∼40 pptv in the first 6 hours in a base case scenario, with typical increases of [HCOOH] ranging from 20–60 pptv over a period of 96 hours) whereas its effect on other important trace species (i.e. O3, NOx, HOx and HCHO) was negligible. Carboxylic acid concentrations are at present underestimated by major atmospheric chemical models, and these results indicate that the atmospheric transformation of enols may be an important missing secondary source term for carboxylic acids in the urban troposphere.

Naturally produced hydrocarbons such as isoprene influence air quality and climate. Accounting for circadian control of isoprene emissions helps to bring model simulations of ground-level ozone into closer agreement with observations.

Carbonyl oxides (“Criegee intermediates”), formed in the ozonolysis of alkenes, are key species in tropospheric oxidation of organic molecules and their decomposition provides a non-photolytic source of OH in the atmosphere (Johnson and Marston, Chem. Soc. Rev., 2008, 37, 699, Harrison et al., Sci. Total Environ., 2006, 360, 5, Gab et al., Nature, 1985, 316, 535, ). Recently it was shown that small Criegee intermediates, C.I.’s, react far more rapidly with SO2 than typically represented in tropospheric models, (Welz, Science, 2012, 335, 204, ) which suggested that carbonyl oxides could have a substantial influence on the atmospheric oxidation of SO2. Oxidation of SO2 is the main atmospheric source of sulphuric acid (H2SO4), which is a critical contributor to aerosol formation, although questions remain about the fundamental nucleation mechanism (Sipila et al., Science, 2010, 327, 1243, Metzger et al., Proc. Natl. Acad. Sci. U. S. A., 2010 107, 6646, Kirkby et al., Nature, 2011, 476, 429, ). Non-absorbing atmospheric aerosols, by scattering incoming solar radiation and acting as cloud condensation nuclei, have a cooling effect on climate (Intergovernmental Panel on Climate Change (IPCC), Climate Change 2007: The Physical Science Basis, Cambridge University Press, 2007, ). Here we explore the effect of the Criegees on atmospheric chemistry, and demonstrate that ozonolysis of alkenes via the reaction of Criegee intermediates potentially has a large impact on atmospheric sulphuric acid concentrations and consequently the first steps in aerosol production. Reactions of Criegee intermediates with SO2 will compete with and in places dominate over the reaction of OH with SO2 (the only other known gas-phase source of H2SO4) in many areas of the Earth's surface. In the case that the products of Criegee intermediate reactions predominantly result in H2SO4 formation, modelled particle nucleation rates can be substantially increased by the improved experimentally obtained estimates of the rate coefficients of Criegee intermediate reactions. Using both regional and global scale modelling, we show that this enhancement is likely to be highly variable spatially with local hot-spots in e.g. urban outflows. This conclusion is however contingent on a number of remaining uncertainties in Criegee intermediate chemistry.

A temperature and pressure kinetic study for the CH(3)O(2) + ClO reaction has been performed using the turbulent flow technique with a chemical ionisation mass spectrometry detection system. An Arrhenius expression was obtained for the overall rate coefficient of CH(3)O(2) + ClO reaction: k(10)(T) = (1.96(−0.24)(+0.28)) × 10(-11) exp[(-626 ± 35)/T] cm(3) molecule(-1) s(-1) where the uncertainty associated with the rate coefficient is given at the one standard deviation level. Over a range of pressure (100-200 Torr) and temperature (298-223 K) no pressure dependence is observed. The smaller rate coefficients measured at lower temperatures compared with both previous low temperature studies are believed to arise through the reduction of secondary chemistry and greater sensitivity in terms of reactant detection (hence much lower initial concentrations were employed). These new data reduce the effectiveness of ozone loss cycles involving reaction of CH(3)O(2) + ClO in the polar stratosphere by around a factor of 1.5 and restrict the importance of the reaction to the tropical and extra-tropical clean marine environments in the troposphere.

The impact of the formation of HO2-H2O adducts following reaction between H2O and HO2 and subsequent reaction of this adduct on HOx, H2O2 and O3 as a function of relative humidity in the marine boundary layer has been investigated using a zero-dimensional box model. The results of simulations with different product yields for the reaction of HO2-H2O with HO2 were compared with base case data derived from current recommendations for tropospheric modelling. It is suggested that inclusion of reactions of the HO2-H2O adduct may provide a significant sink for HO2 which has so far not been considered in models of tropospheric chemistry and depending on reaction products may have a significant impact on H2O2 and O3.

Biodiesel use is being promoted worldwide as a green alternative to conventional diesel. A global three-dimensional chemistry transport model is employed to investigate the impact on air quality and global tropospheric composition of adopting biodiesel as a fractional component of diesel use. Five global simulations are conducted where emission changes of hydrocarbons and nitrogen oxides were applied within the model to investigate changes in tropospheric pollutants. Hydrocarbon emission reductions lead to an overall improvement in air quality with reductions in ozone, organic aerosol, aromatic species and PAN. However when the increase in NOx, caused by increased exhaust temperature, is included there is negligible difference in ozone production between mineral diesel and biodiesel blends. The cause of these effects is discussed. [Received: September 30, 2009; Accepted: December 12, 2009]

The Southern Hemisphere (SH) zonal-mean circulation change in response to Antarctic ozone depletion is re-visited by examining a set of the latest model simulations archived for the Chemistry-Climate Model Initiative (CCMI) project. All models reasonably well reproduce Antarctic ozone depletion in the late 20th century. The related SH-summer circulation changes, such as a poleward intensification of westerly jet and a poleward expansion of the Hadley cell, are also well captured. All experiments exhibit quantitatively the same multi-model mean trend, irrespective of whether the ocean is coupled or prescribed. Results are also quantitatively similar to those derived from the Coupled Model Intercomparison Project phase 5 (CMIP5) high-top model simulations in which the stratospheric ozone is mostly prescribed with monthly- and zonally-averaged values. These results suggest that the ozone-hole-induced SH-summer circulation changes are robust across the models irrespective of the specific chemistry-atmosphere-ocean coupling. ISSN:1748-9326 ISSN:1748-9318