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, HO(2), is intimately involved in the oxidation chemistry of the atmosphere. This critical review discusses field measurements of local concentrations of OH and HO(2) 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 HO(2) 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-NO(x) 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 HO(2) 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.

Kinetics of CH2OO Criegee intermediate reactions with SO2, NO2, NO, H2O and CH3CHO and CH2I radical reactions with NO2 are reported as a function of pressure at 295 K. Measurements were made under pseudo-first-order conditions using flash photolysis of CH2I2-O2-N2 gas mixtures in the presence of excess co-reagent combined with monitoring of HCHO reaction products by laser-induced fluorescence (LIF) spectroscopy and, for the reaction with SO2, direct detection of CH2OO by photoionisation mass spectrometry (PIMS). Rate coefficients for CH2OO + SO2 and CH2OO + NO2 are independent of pressure in the ranges studied and are (3.42 ± 0.42) × 10(-11) cm(3) s(-1) (measured between 1.5 and 450 Torr) and (1.5 ± 0.5) × 10(-12) cm(3) s(-1) (measured between 25 and 300 Torr), respectively. The rate coefficient for CH2OO + CH3CHO is pressure dependent, with the yield of HCHO decreasing with increasing pressure. Upper limits of 2 × 10(-13) cm(3) s(-1) and 9 × 10(-17) cm(3) s(-1) are placed on the rate coefficients for CH2OO + NO and CH2OO + H2O, respectively. The upper limit for the rate coefficient for CH2OO + H2O is significantly lower than has been reported previously, with consequences for modelling of atmospheric impacts of CH2OO chemistry.

Abstract. The lifetime of methane is controlled to a very large extent by the abundance of the OH radical. The tropics are a key region for methane removal, with oxidation in the lower tropical troposphere dominating the global methane removal budget (Bloss et al., 2005). In tropical forested environments where biogenic VOC emissions are high and NO x concentrations are low, OH concentrations are assumed to be low due to rapid reactions with sink species such as isoprene. New, simultaneous measurements of OH concentrations and OH reactivity, k OH , in a Borneo rainforest are reported and show much higher OH than predicted, with mean peak concentrations of ∼2.5×10 6 molecule cm −3 (10 min average) observed around solar noon. Whilst j (O 1 D) and humidity were high, low O 3 concentrations limited the OH production from O 3 photolysis. Measured OH reactivity was very high, peaking at a diurnal average of 29.1±8.5 s −1 , corresponding to an OH lifetime of only 34 ms. To maintain the observed OH concentration given the measured OH reactivity requires a rate of OH production approximately 10 times greater than calculated using all measured OH sources. A test of our current understanding of the chemistry within a tropical rainforest was made using a detailed zero-dimensional model to compare with measurements. The model overpredicted the observed HO 2 concentrations and significantly under-predicted OH concentrations. Inclusion of an additional OH source formed as a recycled product of OH iniCorrespondence to: L. K. Whalley (l.k.whalley@leeds.ac.uk) tiated isoprene oxidation improved the modelled OH agreement but only served to worsen the HO 2 model/measurement agreement. To replicate levels of both OH and HO 2 , a process that recycles HO 2 to OH is required; equivalent to the OH recycling effect of 0.74 ppbv of NO. This recycling step increases OH concentrations by 88 % at noon and has wide implications, leading to much higher predicted OH over tropical forests, with a concomitant reduction in the CH 4 lifetime and increase in the rate of VOC degradation.

Abstract. In April-July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforCorrespondence to: C. N. Hewitt (n.hewitt@lancaster.ac.uk) est" (OP3) project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest Published by Copernicus Publications on behalf of the European Geosciences Union. 170 C. N. Hewitt et al.: The OP3 project: introduction, rationale, location characteristics and tools site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO 2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NO x volume mixing ratio (∼100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 10 5 radicals cm −3 , but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.

Abstract. Measurements of HONO were carried out at an urban background site near central London as part of the Clean air for London (ClearfLo) project in summer 2012. Data were collected from 22 July to 18 August 2014, with peak values of up to 1.8 ppbV at night and non-zero values of between 0.2 and 0.6 ppbV seen during the day. A wide range of other gas phase, aerosol, radiation, and meteorological measurements were made concurrently at the same site, allowing a detailed analysis of the chemistry to be carried out. The peak HONO / NO x ratio of 0.04 is seen at ∼ 02:00 UTC, with the presence of a second, daytime, peak in HONO / NO x of similar magnitude to the night-time peak, suggesting a significant secondary daytime HONO source. A photostationary state calculation of HONO involving formation from the reaction of OH and NO and loss from photolysis, reaction with OH, and dry deposition shows a significant underestimation during the day, with calculated values being close to 0, compared to the measurement average of 0.4 ppbV at midday. The addition of further HONO sources from the literature, including dark conversion of NO 2 on surfaces, direct emission, photolysis of ortho-substituted nitrophenols, the postulated formation from the reaction of HO 2 × H 2 O with NO 2 , photolysis of adsorbed HNO 3 on ground and aerosols, and HONO produced by photosensitized conversion of NO 2 on the surface increases the daytime modelled HONO to 0.1 ppbV, still leaving a significant missing daytime source. The missing HONO is plotted against a series of parameters including NO 2 and OH reactivity (used as a proxy for organic material), with little correlation seen. Much better correlation is observed with the product of these species with j (NO 2 ), in particular NO 2 and the product of NO 2 with OH reactivity. This suggests the missing HONO source is in some way related to NO 2 and also requires sunlight. Increasing the photosensitized surface conversion rate of NO 2 by a factor of 10 to a mean daytime first-order loss of ∼ 6 ×10 −5 s −1 (but which varies as a function of j (NO 2 )) closes the daytime HONO budget at all times (apart from the late afternoon), suggesting that urban surfaces may enhance this photosensitized source. The effect of the missing HONO to OH radical production is also investigated and it is shown that the model needs to be constrained to measured HONO in order to accurately reproduce the OH radical measurements.

Observations of the tropical atmosphere are fundamental to the understanding of global changes in air quality, atmospheric oxidation capacity and climate, yet the tropics are under-populated with long-term measurements. The first three years (October 2006 -September 2009) of meteorological, trace gas and particulate data from the global WMO/Global Atmospheric Watch (GAW) Cape Verde Atmospheric Observatory Humberto Duarte Fonseca (CVAO; 16° 51' N, 24° 52' W) are presented, along with a characterisation of the origin and pathways of air masses arriving at the station using the NAME dispersion model and simulations of dust deposition using the COSMO-MUSCAT dust model. The observations show a strong influence from Saharan dust in winter with a maximum in super-micron aerosol and particulate iron and aluminium. The dust model results match the magnitude and daily variations of dust events, but in the region of the CVAO underestimate the measured aerosol optical thickness (AOT) because of contributions from other aerosol. The NAME model also captured the dust events, giving confidence in its ability to correctly identify air mass origins and pathways in this region. Dissolution experiments on collected dust samples showed a strong correlation between soluble Fe and Al and measured solubilities were lower at high atmospheric dust concentrations.Fine mode aerosol at the CVAO contains a significant fraction of non-sea salt components including dicarboxylic acids, methanesulfonic acid and aliphatic amines, all believed to be of oceanic origin. A marine influence is also apparent in the year-round presence of iodine and bromine monoxide (IO and BrO), with IO suggested to be confined mainly to the surface few hundred metres but BrO well mixed in the boundary layer. Enhanced CO 2 and CH 4 and depleted oxygen concentrations are markers for air-sea exchange over the nearby northwest African coastal upwelling area. Long-range transport results in generally higher levels of O 3 and anthropogenic non-methane hydrocarbons (NMHC) in air originating from North America. Ozone/CO ratios were highest (up to 0.42) in European air masses that contain relatively less well-aged air. In air heavily influenced by Saharan dust the O 3 /CO ratio was as low as 0.13, possibly indicating O 3 uptake to dust. Nitrogen oxides (NO x and NO y ) show generally higher concentrations in winter when air mass origins are predominantly from Africa. High photochemical activity at the site is shown by maximum spring/summer concentrations of OH and HO 2 of 9 × 10 6 molecule cm -3 and 6 × 10 8 molecule cm -3 , respectively. After the primary photolysis source, the chemistry of IO and BrO, the abundance of HCHO, and aerosol uptake are important for the HO x budget in this region.3

The first nitryl chloride (ClNO 2 ) measurements in the UK were made during the summer 2012 ClearfLo campaign with a chemical ionization mass spectrometer, utilizing an I À ionization scheme.Concentrations of ClNO 2 exceeded detectable limits (11 ppt) every night with a maximum concentration of 724 ppt. A diurnal profile of ClNO 2 peaking between 4 and 5 A.M., decreasing directly after sunrise, was observed. Concentrations of ClNO 2 above the detection limit are generally observed between 8 P.M. and 11 A.M. Different ratios of the production of ClNO 2 :N 2 O 5 were observed throughout with both positive and negative correlations between the two species being reported. The photolysis of ClNO 2 and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. Simultaneous measurements of hydroxyl radicals (OH) using low pressure laser-induced fluorescence and ozone enabled the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O 3 to be compared. For the day with the maximum calculated Cl atom concentration, Cl atoms in the early morning were the dominant oxidant for alkanes and, over the entire day, contributed 15%, 3%, and 26% toward the oxidation of alkanes, alkenes, and alkynes, respectively.

The Clean Air for London (ClearfLo) project provides integrated measurements of the meteorology, composition, and particulate loading of the urban atmosphere in London, United Kingdom, to improve predictive capability for air quality. METEOROLOGY, AIR QUALITY, AND HEALTH IN LONDONThe ClearfLo Project Economic and Social Affairs 2013). Urban populations are exposed to stressful environmental conditions, such as local and nonlocal pollutants, that cause poor air quality and microclimates that exacerbate heat stress during heat waves. These are projected to increase in a warming climate. Our cities are therefore nexus points for several environmental health stresses that we currently face (Rydin et al. 2012) and the interacting issues around sustainability and human health.The purpose of this paper is to introduce the Clean Air for London (ClearfLo) project, which investigates the atmospheric science that underpins these health stresses, with a particular focus on the urban increment in atmospheric drivers. We focused on three atmospheric drivers of environmental health stress in cities, namely, heat, gas-phase pollutants, and particulate matter (PM). Health stresses from the urban atmospheric environment.Heat waves have an impact on human health. Populations typically display an optimal temperature range at which the (daily or weekly) mortality rate is lowest. Mortality rates rise as temperatures exceed this optimal range (e.g., Rydin et al. 2012). The 2003 European heat wave (Stedman 2004) in combination with air pollution was responsible for more than 2000 excess deaths in the United Kingdom (Johnson et al. 2005). Under a warming climate, the risks posed by heat stress are predicted to increase (Hacker et al. 2005). People living in urban environments are exposed to higher temperatures than in nonurban regions. Thus, heat-related deaths could be higher within urban areas (Mavrogianni et al. 2011). Hence, ClearfLo is concerned with measuring the factors controlling the urban atmospheric boundary layer, that is, the surface energy balance.The World Health Organization (WHO) reported (WHO 2006) that the strongest effects of air quality 779MAY 2015 AMERICAN METEOROLOGICAL SOCIETY | on health are attributable to PM, followed by ozone (O 3 ) and nitrogen dioxide (NO 2 ). A recent report (Guerreiro et al. 2013) indicates that in 2011 up to 88% of the urban population in Europe was exposed to concentrations exceeding the WHO air quality guidelines for PM 10 (defined as particles that pass through a size-selective inlet with a 50% efficiency cutoff at 10-µm aerodynamic diameter, representative of the inhalable fraction). It is estimated that a reduction of PM 10 to the WHO annual-mean guideline of 20 µg m −3 would reduce attributable deaths per year in Europe by 22,000. Further, this would lead to a substantial improvement in the quality of life for millions with a preexisting respiratory or cardiovascular disease (COMEAP 2010).Epidemiological studies consistently demonstrate an association between the PM mass concentr...