The hydroxyl radical, OH, initiates the removal of the majority of trace gases in the atmosphere, and together with the closely coupled species, the hydroperoxy radical, HO2, is intimately involved in the oxidation chemistry of the atmosphere. This critical review discusses field measurements of local concentrations of OH and HO2 radicals in the troposphere, and in particular the comparisons that have been made with numerical model calculations containing a detailed chemical mechanism. The level of agreement between field measurements of OH and HO2 concentrations and model calculations for a given location provides an indication of the degree of understanding of the underlying oxidation chemistry. We review the measurement-model comparisons for a range of different environments sampled from the ground and from aircraft, including the marine boundary layer, continental low-NOx regions influenced by biogenic emissions, the polluted urban boundary layer, and polar regions. Although good agreement is found for some environments, there are significant discrepancies which remain unexplained, a notable example being unpolluted, forested regions. OH and HO2 radicals are difficult species to measure in the troposphere, and we also review changes in detection methodology, quality assurance procedures such as instrument intercomparisons, and potential interferences.

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Tropospheric OH and HO2 radicals: field measurements and model comparisons.

The growth of the smallest atmospheric particles to sizes at which they may act as seeds for cloud droplets is a key step linking aerosols to clouds and climate. A synthesis of research indicates that the mechanisms controlling this growth depend on the size of the growing particle. Aerosols have a strong, yet poorly quantified, effect on climate. The growth of the smallest atmospheric particles from diameters in the nanometre range to sizes at which they may act as seeds for cloud droplets is a key step linking aerosols to clouds and climate. In many environments, atmospheric nanoparticles grow by taking up organic compounds that are derived from biogenic hydrocarbon emissions. Several mechanisms may control this uptake. Condensation of low-volatility vapours and formation of organic salts probably dominate the very first steps of growth in particles close to 1 nm in diameter. As the particles grow further, formation of organic polymers and effects related to the phase of the particle probably become increasingly important. We suggest that dependence of particle growth mechanisms on particle size needs to be investigated more systematically.

The contribution of organics to atmospheric nanoparticle growth

Contribution of organics to atmospheric nanoparticle growth

The reaction of Criegee intermediates (CI) with NO and RO2 radicals is studied for the first time by theoretical methodologies; additionally, the reaction of CI with SO2 molecules is re-examined. The reaction of CI with NO was found to be slow, with a distinct energy barrier. Their reaction with RO2 radicals proceeds by the formation of a pre-reactive complex followed by addition of the RO2 radical on the CI carbon over a submerged barrier, leading to a larger peroxy radical and opening the possibility for oligomer formation in agreement with experiment. The impact of singlet biradicals on the reaction of CI with SO2 is examined, finding a different reaction mechanism compared to earlier work. For larger CI, the reaction with SO2 at atmospheric pressures mainly yields thermalized sulfur-bearing secondary ozonides. The fate of the CI in the atmosphere is examined in detail, based on observed concentration of a multitude of coreactants in the atmosphere, and estimated rate coefficients available from literature data. The impact of SCI on tropospheric chemistry is discussed.

The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere

The complexity of the linkages between ozone depletion, UV-B radiation and climate change has become more apparent.

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Environmental effects of ozone depletion and its interactions with climate change: progress report, 2011

. Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiala United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

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Observation and modelling of HOx radicals in a boreal forest

. This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiala, Finland from 12 July–12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urban anthropogenic pollution (pentane and SO2) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures.

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R. Oswald

Papers

Observation and modelling of HOx radicals in a boreal forest

The summertime Boreal forest field measurement intensive (HUMPPA-COPEC-2010): an overview of meteorological and chemical influences