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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.

The impact of including a more detailed VOC oxidation scheme (CRI v2-R5) with a multi-generational approach for simulating tropospheric acetone is investigated using a 3-D global model, STOCHEM-CRI. The CRI v2-R5 mechanism contains photochemical production of acetone from monoterpenes which account for 64% (46.8 Tg/yr) of the global acetone sources in STOCHEM-CRI. Both photolysis and oxidation by OH in the troposphere contributes equally (42%, each) and dry deposition contributes 16% of the atmospheric sinks of acetone. The tropospheric life-time and the global burden of acetone are found to be 18 days and 3.5 Tg, respectively, these values being close to those reported in the study of Jacob et al. (2002). A dataset of aircraft campaign measurements are used to evaluate the inclusion of acetone formation from monoterpenes in the CRI v2-R5 mechanism used in STOCHEM-CRI. The overall comparison between measurements and models show that the parameterised approach in STOCHEM-NAM (no acetone formation from monoterpenes) underpredicts the mixing ratios of acetone in the atmosphere. However, using a detailed monoterpene oxidation mechanism forming acetone has brought the STOCHEM-CRI into closer agreement with measurements with an improvement in the vertical simulation of acetone. The annual mean surface distribution of acetone simulated by the STOCHEM-CRI shows a peak over forested regions where there are large biogenic emissions and high levels of photochemical activity. Year-long observations of acetone and methanol at the Mace Head research station in Ireland are compared with the simulated acetone and methanol produced by the STOCHEM-CRI and found to produce good overall agreement between model and measurements. The seasonal variation of model and measured acetone levels at Mace Head, California, New Hampshire and Minnesota show peaks in summer and dips in winter, suggesting that photochemical production may have the strongest effect on its seasonal trend.

Increasing the complexity of the chemistry scheme in the global chemistry transport model STOCHEM to STOCHEM-CRI (Utembe et al., 2010) leads to an increase in NOx as well as ozone resulting in higher NO3 production over forested regions and regions impacted by anthropogenic emission. Peak NO3 is located over the continents near NOx emission sources. NO3 is formed in the main by the reaction of NO2 with O3, and the significant losses of NO3 are due to the photolysis and the reactions with NO and VOCs. Isoprene is an important biogenic VOC, and the possibility of HOx recycling via isoprene chemistry and other mechanisms such as the reaction of RO2 with HO2 has been investigated previously (Archibald et al., 2010a). The importance of including HOx recycling processes on the global budget of NO3 for present and pre-industrial scenarios has been studied using STOCHEM-CRI, and the results are compared. The large increase (up to 60% for present and up to 80% for pre-industrial) in NO3 is driven by the reduced lifetime of emitted VOCs because of the increase in the HOx concentration. The maximum concentration changes (up to 15ppt) for NO3 from pre-industrial to present day are found at the surface between 30oN and 60oN because of the increase in NOx concentrations in the present day integrations.

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.