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OH, HO2, total and partially speciated RO2, and OH reactivity (kOH′) were measured during the July 2015 ICOZA (Integrated Chemistry of OZone in the Atmosphere) project that took place at a coastal site in north Norfolk, UK. Maximum measured daily OH, HO2 and total RO2 radical concentrations were in the range 2.6–17 × 106, 0.75–4.2 × 108 and 2.3–8.0 × 108 molec. cm−3, respectively. kOH′ ranged from 1.7 to 17.6 s−1, with a median value of 4.7 s−1. ICOZA data were split by wind direction to assess differences in the radical chemistry between air that had passed over the North Sea (NW–SE sectors) and that over major urban conurbations such as London (SW sector). A box model using the Master Chemical Mechanism (MCMv3.3.1) was in reasonable agreement with the OH measurements, but it overpredicted HO2 observations in NW–SE air in the afternoon by a factor of ∼ 2–3, although slightly better agreement was found for HO2 in SW air (factor of ∼ 1.4–2.0 underprediction). The box model severely underpredicted total RO2 observations in both NW–SE and SW air by factors of ∼ 8–9 on average. Measured radical and kOH′ levels and measurement–model ratios displayed strong dependences on NO mixing ratios, with the results suggesting that peroxy radical chemistry is not well understood under high-NOx conditions. The simultaneous measurement of OH, HO2, total RO2 and kOH′ was used to derive experimental (i.e. observationally determined) budgets for all radical species as well as total ROx (i.e. OH + HO2 + RO2). In NW–SE air, the ROx budget could be closed during the daytime within experimental uncertainty, but the rate of OH destruction exceeded the rate of OH production, and the rate of HO2 production greatly exceeded the rate of HO2 destruction, while the opposite was true for RO2. In SW air, the ROx budget analysis indicated missing daytime ROx sources, but the OH budget was balanced, and the same imbalances were found with the HO2 and RO2 budgets as in NW–SE air. For HO2 and RO2, the budget imbalances were most severe at high-NO mixing ratios, and the best agreement between HO2 and RO2 rates of production and destruction rates was found when the RO2 + NO rate coefficient was reduced by a factor of 5. A photostationary-steady-state (PSS) calculation underpredicted daytime OH in NW–SE air by ∼ 35 %, whereas agreement (∼ 15 %) was found within instrumental uncertainty (∼ 26 % at 2σ) in SW air. The rate of in situ ozone production (P(Ox)) was calculated from observations of ROx, NO and NO2 and compared to that calculated from MCM-modelled radical concentrations. The MCM-calculated P(Ox) significantly underpredicted the measurement-calculated P(Ox) in the morning, and the degree of underprediction was found to scale with NO.

In situ field measurements of glyoxal at the surface in the tropical marine boundary layer have been made with a temporal resolution of a few minutes during two 4-week campaigns in June–July and August–September 2014 at the Cape Verde Atmospheric Observatory (CVAO; 16∘52′ N, 24∘52′ W). Using laser-induced phosphorescence spectroscopy with an instrumental detection limit of ∼1 pptv (1 h averaging), volume mixing ratios up to ∼10 pptv were observed, with 24 h averaged mixing ratios of 4.9 and 6.3 pptv observed during the first and second campaigns, respectively. Some diel behaviour was observed, but this was not marked. A box model using the detailed Master Chemical Mechanism (version 3.2) and constrained with detailed observations of a suite of species co-measured at the observatory was used to calculate glyoxal mixing ratios. There is a general model underestimation of the glyoxal observations during both campaigns, with mean midday (11:00–13:00) observed-to-modelled ratios for glyoxal of 3.2 and 4.2 for the two campaigns, respectively, and higher ratios at night. A rate of production analysis shows the dominant sources of glyoxal in this environment to be the reactions of OH with glycolaldehyde and acetylene, with a significant contribution from the reaction of OH with the peroxide HC(O)CH2OOH, which itself derives from OH oxidation of acetaldehyde. Increased mixing ratios of acetaldehyde, which is unconstrained and potentially underestimated in the base model, can significantly improve the agreement between the observed and modelled glyoxal during the day. Mean midday observed-to-modelled glyoxal ratios decreased to 1.3 and 1.8 for campaigns 1 and 2, respectively, on constraint to a fixed acetaldehyde mixing ratio of 200 pptv, which is consistent with recent airborne measurements near CVAO. However, a significant model under-prediction remains at night. The model showed limited sensitivity to changes in deposition rates of model intermediates and the uptake of glyoxal onto aerosol compared with sensitivity to uncertainties in chemical precursors. The midday (11:00–13:00) mean modelled glyoxal mixing ratio decreased by factors of 0.87 and 0.90 on doubling the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively, and increased by factors of 1.10 and 1.06 on halving the deposition rates of model intermediates and aerosol uptake of glyoxal, respectively. Although measured levels of monoterpenes at the site (total of ∼1 pptv) do not significantly influence the model calculated levels of glyoxal, transport of air from a source region with high monoterpene emissions to the site has the potential to give elevated mixing ratios of glyoxal from monoterpene oxidation products, but the values are highly sensitive to the deposition rates of these oxidised intermediates. A source of glyoxal derived from production in the ocean surface organic microlayer cannot be ruled out on the basis of this work and may be significant at night.

Hydroxyl (OH) and hydroperoxy (HO2) radicals are central to the understanding of atmospheric chemistry. Owing to their short lifetimes, these species are frequently used to test the accuracy of model predictions and their underlying chemical mechanisms. In forested environments, laser-induced fluorescence–fluorescence assay by gas expansion (LIF–FAGE) measurements of OH have often shown substantial disagreement with model predictions, suggesting the presence of unknown OH sources in such environments. However, it is also possible that the measurements have been affected by instrumental artefacts, due to the presence of interfering species that cannot be discriminated using the traditional method of obtaining background signals via modulation of the laser excitation wavelength (“OHwave”). The interference hypothesis can be tested by using an alternative method to determine the OH background signal, via the addition of a chemical scavenger prior to sampling of ambient air (“OHchem”). In this work, the Leeds FAGE instrument was modified to include such a system to facilitate measurements of OHchem, in which propane was used to selectively remove OH from ambient air using an inlet pre-injector (IPI). The IPI system was characterised in detail, and it was found that the system did not reduce the instrument sensitivity towards OH ( 99 %) without the removal of OH formed inside the fluorescence cell (∼4×105 molec. cm−3 under typical atmospheric conditions of [O3] =50 ppbv and [H2O] =1 %. Laboratory experiments to investigate potential interferences from products of isoprene ozonolysis did result in interference signals, but these were negligible when extrapolated down to ambient ozone and isoprene levels. The interference from NO3 radicals was also tested but was found to be insignificant in our system. The Leeds IPI module was deployed during three separate field intensives that took place in summer at a coastal site in the UK and both in summer and winter in the megacity of Beijing, China, allowing for investigations of ambient OH interferences under a wide range of chemical and meteorological conditions. Comparisons of ambient OHchem measurements to the traditional OHwave method showed excellent agreement, with OHwave vs OHchem slopes of 1.05–1.16 and identical behaviour on a diel basis, consistent with laboratory interference tests. The difference between OHwave and OHchem (“OHint”) was found to scale non-linearly with OHchem, resulting in an upper limit interference of (5.0±1.4) ×106 molec. cm−3 at the very highest OHchem concentrations measured (23×106 molec. cm−3), accounting for ∼14 %–21 % of the total OHwave signal.

The chemistry of the halogen species bromine and iodine has a range of impacts on tropospheric composition, and can affect oxidising capacity in a number of ways. However, recent studies disagree on the overall sign of the impacts of halogens on the oxidising capacity of the troposphere. We present simulations of OH and HO2 radicals for comparison with observations made in the remote tropical ocean boundary layer during the Seasonal Oxidant Study at the Cape Verde Atmospheric Observatory in 2009. We use both a constrained box model, using detailed chemistry derived from the Master Chemical Mechanism (v3.2), and the three-dimensional global chemistry transport model GEOS-Chem. Both model approaches reproduce the diurnal trends in OH and HO2. Absolute observed concentrations are well reproduced by the box model but are overpredicted by the global model, potentially owing to incomplete consideration of oceanic sourced radical sinks. The two models, however, differ in the impacts of halogen chemistry. In the box model, halogen chemistry acts to increase OH concentrations (by 9.8 % at midday at the Cape Verde Atmospheric Observatory), while the global model exhibits a small increase in OH at the Cape Verde Atmospheric Observatory (by 0.6 % at midday) but overall shows a decrease in the global annual mass-weighted mean OH of 4.5 %. These differences reflect the variety of timescales through which the halogens impact the chemical system. On short timescales, photolysis of HOBr and HOI, produced by reactions of HO2 with BrO and IO, respectively, increases the OH concentration. On longer timescales, halogen-catalysed ozone destruction cycles lead to lower primary production of OH radicals through ozone photolysis, and thus to lower OH concentrations. The global model includes more of the longer timescale responses than the constrained box model, and overall the global impact of the longer timescale response (reduced primary production due to lower O3 concentrations) overwhelms the shorter timescale response (enhanced cycling from HO2 to OH), and thus the global OH concentration decreases. The Earth system contains many such responses on a large range of timescales. This work highlights the care that needs to be taken to understand the full impact of any one process on the system as a whole.

Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (±0.3) × 10−11 cm3 molecule−1 s−1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

One geoengineering mitigation strategy for global temperature rises resulting from the increased concentrations of greenhouse gases is to inject particles into the stratosphere to scatter solar radiation back to space, with TiO2 particles emerging as a possible candidate. Uptake coefficients of HO2, γ(HO2), onto sub-micrometre TiO2 particles were measured at room temperature and different relative humidities (RHs) using an atmospheric pressure aerosol flow tube coupled to a sensitive HO2 detector. Values of γ(HO2) increased from 0.021 ± 0.001 to 0.036 ± 0.007 as the RH was increased from 11 to 66 %, and the increase in γ(HO2) correlated with the number of monolayers of water surrounding the TiO2 particles. The impact of the uptake of HO2 onto TiO2 particles on stratospheric concentrations of HO2 and O3 was simulated using the TOMCAT three-dimensional chemical transport model. The model showed that, when injecting the amount of TiO2 required to achieve the same cooling effect as the Mt Pinatubo eruption, heterogeneous reactions between HO2 and TiO2 would have a negligible effect on stratospheric concentrations of HO2 and O3.

We report the first measurements of HO2 uptake coefficients, γ, for secondary organic aerosol (SOA) particles and for the well-studied model compound sucrose which we doped with copper(II). Above 65 % relative humidity (RH), γ for copper(II)-doped sucrose aerosol particles equalled the surface mass accommodation coefficient α  =  0.22 ± 0.06, but it decreased to γ  =  0.012 ± 0.007 upon decreasing the RH to 17 %. The trend of γ with RH can be explained by an increase in aerosol viscosity and the contribution of a surface reaction, as demonstrated using the kinetic multilayer model of aerosol surface and bulk chemistry (KM-SUB). At high RH the total uptake was driven by reaction in the near-surface bulk and limited by mass accommodation, whilst at low RH it was limited by surface reaction. SOA from two different precursors, α-pinene and 1,3,5-trimethylbenzene (TMB), was investigated, yielding low uptake coefficients of γ  γ  =  0.004 ± 0.002, respectively. It is postulated that the larger values measured for TMB-derived SOA compared to α-pinene-derived SOA are either due to differing viscosity, a different liquid water content of the aerosol particles, or an HO2 + RO2 reaction occurring within the aerosol particles.

OH reactivity (k′OH) is the total pseudo-first-order loss rate coefficient describing the removal of OH radicals to all sinks in the atmosphere, and is the inverse of the chemical lifetime of OH. Measurements of ambient OH reactivity can be used to discover the extent to which measured OH sinks contribute to the total OH loss rate. Thus, OH reactivity measurements enable determination of the comprehensiveness of measurements used in models to predict air quality and ozone production, and, in conjunction with measurements of OH radical concentrations, to assess our understanding of OH production rates. In this work, we describe the design and characterisation of an instrument to measure OH reactivity using laser flash photolysis coupled to laser-induced fluorescence (LFP-LIF) spectroscopy. The LFP-LIF technique produces OH radicals in isolation, and thus minimises potential interferences in OH reactivity measurements owing to the reaction of HO2 with NO which can occur if HO2 is co-produced with OH in the instrument. Capabilities of the instrument for ambient OH reactivity measurements are illustrated by data collected during field campaigns in London, UK, and York, UK. The instrumental limit of detection for k′OH was determined to be 1.0 s−1 for the campaign in London and 0.4 s−1 for the campaign in York. The precision, determined by laboratory experiment, is typically −1 for most ambient measurements of OH reactivity. Total uncertainty in ambient measurements of OH reactivity is ∼ 6 %. We also present the coupling and characterisation of the LFP-LIF instrument to an atmospheric chamber for measurements of OH reactivity during simulated experiments, and provide suggestions for future improvements to OH reactivity LFP-LIF instruments.

Measurements of the radical species OH and HO2 were made using the fluorescence assay by gas expansion (FAGE) technique during a series of night-time and daytime flights over the UK in summer 2010 and winter 2011. OH was not detected above the instrument's 1σ limit of detection during any of the night-time flights or during the winter daytime flights, placing upper limits on [OH] of 1.8 × 106 molecule cm−3 and 6.4 × 105 molecule cm−3 for the summer and winter flights, respectively. HO2 reached a maximum concentration of 3.2 × 108 molecule cm−3 (13.6 pptv) during a night-time flight on 20 July 2010, when the highest concentrations of NO3 and O3 were also recorded. An analysis of the rates of reaction of OH, O3, and the NO3 radical with measured alkenes indicates that the summer night-time troposphere can be as important for the processing of volatile organic compounds (VOCs) as the winter daytime troposphere. An analysis of the instantaneous rate of production of HO2 from the reactions of O3 and NO3 with alkenes has shown that, on average, reactions of NO3 dominated the night-time production of HO2 during summer and reactions of O3 dominated the night-time HO2 production during winter.

The calibration of field instruments used to measure concentrations of OH and HO2 worldwide has traditionally relied on a single method utilising the photolysis of water vapour in air in a flow tube at atmospheric pressure. Here the calibration of two FAGE (fluorescence assay by gaseous expansion) apparatuses designed for HOx (OH and HO2) measurements have been investigated as a function of external pressure using two different laser systems. The conventional method of generating known concentrations of HOx from H2O vapour photolysis in a turbulent flow tube impinging just outside the FAGE sample inlet has been used to study instrument sensitivity as a function of internal fluorescence cell pressure (1.8–3.8 mbar). An increase in the calibration constants CHO and CHO2 with pressure was observed, and an empirical linear regression of the data was used to describe the trends, with ΔCHO = (17 ± 11) % and ΔCHO2 = (31.6 ± 4.4)% increase per millibar air (uncertainties quoted to 2σ). Presented here are the first direct measurements of the FAGE calibration constants as a function of external pressure (440–1000 mbar) in a controlled environment using the University of Leeds HIRAC chamber (Highly Instrumented Reactor for Atmospheric Chemistry). Two methods were used: the temporal decay of hydrocarbons for calibration of OH, and the kinetics of the second-order recombination of HO2 for HO2 calibrations. Over comparable conditions for the FAGE cell, the two alternative methods are in good agreement with the conventional method, with the average ratio of calibration factors (conventional : alternative) across the entire pressure range, COH(conv)/COH(alt) = 1.19 ± 0.26 and CHO2(conv)/CHO2(alt) = 0.96 ± 0.18 (2σ). These alternative calibration methods currently have comparable systematic uncertainties to the conventional method: ~ 28% and ~ 41% for the alternative OH and HO2 calibration methods respectively compared to 35% for the H2O vapour photolysis method; ways in which these can be reduced in the future are discussed. The good agreement between the very different methods of calibration leads to increased confidence in HOx field measurements and particularly in aircraft-based HOx measurements, where there are substantial variations in external pressure, and assumptions are made regarding loss rates on inlets as a function of pressure.

The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO2 by ~200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3x=NO3+N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3+VOCs (volatile organic compounds) and NO3+RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2+RO2 reactions, heterogeneous processes and production of HNO3 from OH+NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5=0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

OH (hydroxyl radical) reactivity, the inverse of the chemical lifetime of the hydroxyl radical, was measured for 12 days in April 2008 within a tropical rainforest on Borneo as part of the OP3 (Oxidant and Particle Photochemical Processes) project. The maximum observed value was 83.8 ± 26.0 s−1 with the campaign averaged noontime maximum being 29.1 ± 8.5 s−1. The maximum OH reactivity calculated using the diurnally averaged concentrations of observed sinks was ~ 18 s−1, significantly less than the observations, consistent with other studies in similar environments. OH reactivity was dominated by reaction with isoprene (~ 30%). Numerical simulations of isoprene oxidation using the Master Chemical Mechanism (v3.2) in a highly simplified physical and chemical environment show that the steady state OH reactivity is a linear function of the OH reactivity due to isoprene alone, with a maximum multiplier, to account for the OH reactivity of the isoprene oxidation products, being equal to the number of isoprene OH attackable bonds (10). Thus the emission of isoprene constitutes a significantly larger emission of reactivity than is offered by the primary reaction with isoprene alone, with significant scope for the secondary oxidation products of isoprene to constitute the observed missing OH reactivity. A physically and chemically more sophisticated simulation (including physical loss, photolysis, and other oxidants) showed that the calculated OH reactivity is reduced by the removal of the OH attackable bonds by other oxidants and photolysis, and by physical loss (mixing and deposition). The calculated OH reactivity is increased by peroxide cycling, and by the OH concentration itself. Notable in these calculations is that the accumulated OH reactivity from isoprene, defined as the total OH reactivity of an emitted isoprene molecule and all of its oxidation products, is significantly larger than the reactivity due to isoprene itself and critically depends on the chemical and physical lifetimes of intermediate species. When constrained to the observed diurnally averaged concentrations of primary VOCs (volatile organic compounds), O3, NOx and other parameters, the model underestimated the observed diurnal mean OH reactivity by 30%. However, it was found that (1) the short lifetimes of isoprene and OH, compared to those of the isoprene oxidation products, lead to a large variability in their concentrations and so significant variation in the calculated OH reactivity; (2) uncertainties in the OH chemistry in these high isoprene environments can lead to an underestimate of the OH reactivity; (3) the physical loss of species that react with OH plays a significant role in the calculated OH reactivity; and (4) a missing primary source of reactive carbon would have to be emitted at a rate equivalent to 50% that of isoprene to account for the missing OH sink. Although the presence of unmeasured primary emitted VOCs contributing to the measured OH reactivity is likely, evidence that these primary species account for a significant fraction of the unmeasured reactivity is not found. Thus the development of techniques for the measurement of secondary multifunctional carbon compounds is needed to close the OH reactivity budget.

Field measurements of the hydroxyl radical, OH, are crucial for our understanding of tropospheric chemistry. However, observations of this key atmospheric species in the tropical marine boundary layer, where the warm, humid conditions and high solar irradiance lend themselves favourably to production, are sparse. The Seasonal Oxidant Study at the Cape Verde Atmospheric Observatory in 2009 allowed, for the first time, seasonal measurements of both OH and HO2 in a clean (i.e. low NOx), tropical marine environment. It was found that concentrations of OH and HO2 were typically higher in the summer months (June, September), with maximum daytime concentrations of ~9 × 106 and 4 × 108 molecule cm−3, respectively – almost double the values in winter (late February, early March). HO2 was observed to persist at ~107 molecule cm−3 through the night, but there was no strong evidence of nighttime OH, consistent with previous measurements at the site in 2007. HO2 was shown to have excellent correlations (R2 ~ 0.90) with both the photolysis rate of ozone, J(O1D), and the primary production rate of OH, P(OH), from the reaction of O(1D) with water vapour. The analogous relations of OH were not so strong (R2 ~ 0.6), but the coefficients of the linear correlation with J(O1D) in this study were close to those yielded from previous works in this region, suggesting that the chemical regimes have similar impacts on the concentration of OH. Analysis of the variance of OH and HO2 across the Seasonal Oxidant Study suggested that ~70% of the total variance could be explained by diurnal behaviour, with ~30% of the total variance being due to changes in air mass.

The first in situ point observations of iodine monoxide (IO) at a clean marine site were made using a laser-induced fluorescence instrument deployed at Mace Head, Ireland in August 2007. IO mixing ratios of up to 49.8 pptv (equivalent to pmol mol−1; 1 s average) were observed at day-time low tide, well in excess of previous observed spatially-averaged maxima. A strong anti-correlation of IO mixing ratios with tide height was evident and the high time resolution of the observations showed IO peaked in the hour after low tide. The temporal delay in peak IO compared to low tide has not been observed previously but coincides with the time of peak aerosol number previously observed at Mace Head. A long path-differential optical absorption spectroscopy instrument (with a 2 × 6.8 km folded path across Roundstone Bay) was also based at the site for 3 days during the point measurement observation period. Both instruments show similar temporal trends but the point measurements of IO are a factor of ~6–10 times greater than the spatially averaged IO mixing ratios, providing direct empirical evidence of the presence of inhomogeneities in the IO mixing ratio near the intertidal region.

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 NOx 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 ~2.5×106 molecule cm−3 (10 min average) observed around solar noon. Whilst j(O1D) and humidity were high, low O3 concentrations limited the OH production from O3 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 over-predicted the observed HO2 concentrations and significantly under-predicted OH concentrations. Inclusion of an additional OH source formed as a recycled product of OH initiated isoprene oxidation improved the modelled OH agreement but only served to worsen the HO2 model/measurement agreement. To replicate levels of both OH and HO2, a process that recycles HO2 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 CH4 lifetime and increase in the rate of VOC degradation.

Forests are the dominant source of volatile organic compounds into the atmosphere, with isoprene being the most significant species. The oxidation chemistry of these compounds is a significant driver of local, regional and global atmospheric composition. Observations made over Borneo during the OP3 project in 2008, together with an observationally constrained box model are used to assess our understanding of this oxidation chemistry. In line with previous work in tropical forests, we find that the standard model based on MCM chemistry significantly underestimates the observed OH concentrations. Geometric mean observed to modelled ratios of OH and HO2 in airmasses impacted with isoprene are 5.32−4.43+3.68 and 1.18−0.30+0.30 respectively, with 68 % of the observations being within the specified variation. We implement a variety of mechanistic changes into the model, including epoxide formation and unimolecular decomposition of isoprene peroxy radicals, and assess their impact on the model success. We conclude that none of the current suggestions can simultaneously remove the bias from both OH and HO2 simulations and believe that detailed laboratory studies are now needed to resolve this issue.

We demonstrate a new instrument for in situ detection of atmospheric iodine atoms and molecules based on atomic and molecular resonance and off-resonance ultraviolet fluorescence excited by lamp emission. The instrument combines the robustness, light weight, low power consumption and efficient excitation of radio-frequency discharge light sources with the high sensitivity of the photon counting technique. Calibration of I2 fluorescence is achieved via quantitative detection of the molecule by Incoherent Broad Band Cavity-enhanced Absorption Spectroscopy. Atomic iodine fluorescence signal is calibrated by controlled broad band photolysis of known I2 concentrations in the visible spectral range at atmospheric pressure. The instrument has been optimised in laboratory experiments to reach detection limits of 1.2 pptv for I atoms and 13 pptv for I2, for S/N = 1 and 10 min of integration time. The ROFLEX system has been deployed in a field campaign in northern Spain, representing the first concurrent observation of ambient mixing ratios of iodine atoms and molecules in the 1–350 pptv range.

Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis) campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE) and total peroxy radicals (RO2* = HO2+ΣRO2, R = organic chain) by two similar instruments based on the peroxy radical chemical amplification (PeRCA) technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously. Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

Aircraft OH and HO2 measurements made over West Africa during the AMMA field campaign in summer 2006 have been investigated using a box model constrained to observations of long-lived species and physical parameters. "Good" agreement was found for HO2 (modelled to observed gradient of 1.23 ± 0.11). However, the model significantly overpredicts OH concentrations. The reasons for this are not clear, but may reflect instrumental instabilities affecting the OH measurements. Within the model, HOx concentrations in West Africa are controlled by relatively simple photochemistry, with production dominated by ozone photolysis and reaction of O(1D) with water vapour, and loss processes dominated by HO2 + HO2 and HO2 + RO2. Isoprene chemistry was found to influence forested regions. In contrast to several recent field studies in very low NOx and high isoprene environments, we do not observe any dependence of model success for HO2 on isoprene and attribute this to efficient recycling of HOx through RO2 + NO reactions under the moderate NOx concentrations (5–300 ppt NO in the boundary layer, median 76 ppt) encountered during AMMA. This suggests that some of the problems with understanding the impact of isoprene on atmospheric composition may be limited to the extreme low range of NOx concentrations.

The hydroxyl radical (OH) plays a key role in the oxidation of trace gases in the troposphere. However, observations of OH and the closely related hydroperoxy radical (HO2) have been sparse, especially in the tropics. Based on a low-pressure laser-induced fluorescence technique (FAGE – Fluorescence Assay by Gas Expansion), an instrument has been developed to measure OH and HO2 aboard the Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft. During the African Monsoon Multidisciplinary Analyses (AMMA) campaign, observations of OH and HO2 (HOx) were made in the boundary layer and free troposphere over West Africa on 13 flights during July and August 2006. Mixing ratios of both OH and HO2 were found to be highly variable, but followed a diurnal cycle: OH varied from 1.3 pptv to below the instrumental limit of detection, with a median mixing ratio of 0.17 pptv. HO2 varied from 42.7 pptv to below the limit of detection, with a median mixing ratio of 8.0 pptv. A median HO2/OH ratio of 95 was observed. Daytime OH observations were compared with the primary production rate of OH from ozone photolysis in the presence of water vapour. Daytime HO2 observations were generally reproduced by a simple steady-state HOx calculation, where HOx was assumed to be formed from the primary production of OH and lost through HO2 self-reaction. Deviations between the observations and this simple model were found to be grouped into a number of specific cases: (a) within cloud, (b) in the presence of high levels of isoprene in the boundary layer and (c) within a biomass burning plume. HO2 was sampled in and around cloud, with significant short-lived reductions of HO2 observed. Up to 9 pptv of HO2 was observed at night, with HO2 above 6 pptv observed at altitudes above 6 km. In the forested boundary layer, HO2 was underestimated by a steady state calculation at altitudes below 500 m but overestimated between 500 m and 2 km. In a biomass burning plume, observed HO2 concentrations were significantly below those calculated.

Point source measurements of IO by laser induced fluorescence spectroscopy were made at a semi-polluted coastal location during the Reactive Halogens in the Marine Boundary Layer (RHaMBLe) campaign in September 2006. The site, on the NW French coast in Roscoff, was characterised by extensive intertidal macroalgae beds which were exposed at low tide. The closest known iodine active macroalgae beds were at least 300 m from the measurement point. From 20 days of measurements, IO was observed above the instrument limit of detection on 14 days, of which a clear diurnal profile was observed on 11 days. The maximum IO mixing ratio was 30.0 pptv (10 s integration period) during the day, amongst the highest concentrations ever observed in the atmosphere, and 1–2 pptv during the night. IO concentrations were strongly dependent on tidal height, the intensity of solar irradiation and meteorological conditions. An intercomparison of IO measurements made using point source and spatially averaged DOAS instruments confirms the presence of hot-spots of IO caused by an inhomogeneous distribution of macroalgae. The co-incident, point source measurement of IO and ultra fine particles (2.5 nm≥d≥10 nm) displayed a strong correlation, providing evidence that IO is involved in the production pathway of ultra fine particles at coastal locations. Finally, a modelling study shows that high IO concentrations which are likely to be produced in a macrolagae rich environment can significantly perturb the concentrations of OH and HO2 radicals. The effect of IO on HOx is reduced as NOx concentrations increase.

This paper presents a summary of the measurements made during the heavily-instrumented Reactive Halogens in the Marine Boundary Layer (RHaMBLe) coastal study in Roscoff on the North West coast of France throughout September 2006. It was clearly demonstrated that iodine-mediated coastal particle formation occurs, driven by daytime low tide emission of molecular iodine, I2, by macroalgal species fully or partially exposed by the receding waterline. Ultrafine particle concentrations strongly correlate with the rapidly recycled reactive iodine species, IO, produced at high concentrations following photolysis of I2. The heterogeneous macroalgal I2 sources lead to variable relative concentrations of iodine species observed by path-integrated and in situ measurement techniques. Apparent particle emission fluxes were associated with an enhanced apparent depositional flux of ozone, consistent with both a direct O3 deposition to macroalgae and involvement of O3 in iodine photochemistry and subsequent particle formation below the measurement height. The magnitude of the particle formation events was observed to be greatest at the lowest tides with the highest concentrations of ultrafine particles growing to the largest sizes, probably by the condensation of anthropogenically-formed condensable material. At such sizes the particles should be able to act as cloud condensation nuclei at reasonable atmospheric supersaturations.

The NERC UK SOLAS-funded Reactive Halogens in the Marine Boundary Layer (RHaMBLe) programme comprised three field experiments. This manuscript presents an overview of the measurements made within the two simultaneous remote experiments conducted in the tropical North Atlantic in May and June 2007. Measurements were made from two mobile and one ground-based platforms. The heavily instrumented cruise D319 on the RRS Discovery from Lisbon, Portugal to São Vicente, Cape Verde and back to Falmouth, UK was used to characterise the spatial distribution of boundary layer components likely to play a role in reactive halogen chemistry. Measurements onboard the ARSF Dornier aircraft were used to allow the observations to be interpreted in the context of their vertical distribution and to confirm the interpretation of atmospheric structure in the vicinity of the Cape Verde islands. Long-term ground-based measurements at the Cape Verde Atmospheric Observatory (CVAO) on São Vicente were supplemented by long-term measurements of reactive halogen species and characterisation of additional trace gas and aerosol species during the intensive experimental period. This paper presents a summary of the measurements made within the RHaMBLe remote experiments and discusses them in their meteorological and chemical context as determined from these three platforms and from additional meteorological analyses. Air always arrived at the CVAO from the North East with a range of air mass origins (European, Atlantic and North American continental). Trace gases were present at stable and fairly low concentrations with the exception of a slight increase in some anthropogenic components in air of North American origin, though NOx mixing ratios during this period remained below 20 pptv (note the non-IUPAC adoption in this manuscript of pptv and ppbv, equivalent to pmol mol−1 and nmol mol−1 to reflect common practice). Consistency with these air mass classifications is observed in the time series of soluble gas and aerosol composition measurements, with additional identification of periods of slightly elevated dust concentrations consistent with the trajectories passing over the African continent. The CVAO is shown to be broadly representative of the wider North Atlantic marine boundary layer; measurements of NO, O3 and black carbon from the ship are consistent with a clean Northern Hemisphere marine background. Aerosol composition measurements do not indicate elevated organic material associated with clean marine air. Closer to the African coast, black carbon and NO levels start to increase, indicating greater anthropogenic influence. Lower ozone in this region is possibly associated with the increased levels of measured halocarbons, associated with the nutrient rich waters of the Mauritanian upwelling. Bromide and chloride deficits in coarse mode aerosol at both the CVAO and on D319 and the continuous abundance of inorganic gaseous halogen species at CVAO indicate significant reactive cycling of halogens. Aircraft measurements of O3 and CO show that surface measurements are representative of the entire boundary layer in the vicinity both in diurnal variability and absolute levels. Above the inversion layer similar diurnal behaviour in O3 and CO is observed at lower mixing ratios in the air that had originated from south of Cape Verde, possibly from within the ITCZ. ECMWF calculations on two days indicate very different boundary layer depths and aircraft flights over the ship replicate this, giving confidence in the calculated boundary layer depth.

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 rainforest" (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 site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 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:NOx volume mixing ratio (~100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 105 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.

A field instrument utilising the artificial generation of OH radicals in a sliding injector flow-tube reactor with detection by laser-induced fluorescence spectroscopy has been developed to measure the rate of decay of OH by reaction with its atmospheric sinks. The OH reactivity instrument has been calibrated using known concentrations of CO, NO2 and single hydrocarbons in a flow of zero air, and the impact of recycling of OH via the reaction HO2+NO→OH+NO2 on the measured OH reactivity has been quantified. As well as a detailed description of the apparatus, the capabilities of the new instrument are illustrated using representative results from deployment in the semi-polluted marine boundary layer at the Weybourne Atmospheric Observatory, UK, and in a tropical rainforest at the Bukit Atur Global Atmospheric Watch station, Danum Valley, Borneo.

The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and NO2 actinometry have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response at a range of atmospheric conditions.

The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. Between 25 July and 31 August, the concentrations of the hydroxyl radical and the hydroperoxy radical were measured using laser-induced fluorescence at low pressure and the sum of peroxy radicals was measured using the peroxy radical chemical amplifier technique. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. Initiation via OH was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main route for initiation via HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.

OH and HO2 concentrations were measured simultaneously at the Mace Head Atmospheric Research Station in the summer of 2002 during the NAMBLEX (North Atlantic Marine Boundary Layer EXperiment) field campaign. OH was measured by laser-induced fluorescence employing the FAGE (Fluorescence Assay by Gas Expansion) technique, with a mean daytime detection limit of 2.7×105 molecule cm−3 (5 min acquisition period; signal-to-noise ratio = 1). HO2 was detected as OH following its chemical conversion through addition of NO, with a mean detection limit of 4.4×106 molecule cm−3. The diurnal variation of OH was measured on 24 days, and that of HO2 on 17 days. The local solar noon OH concentrations ranged between (3–8)×106 molecule cm−3, with a 24 h mean concentration of 9.1×105 molecule cm−3. The local solar noon HO2 concentrations were (0.9–2.1)×108 molecule cm−3 (3.5–8.2 pptv), with a 24 h mean concentration of 4.2×107 molecule cm−3 (1.6 pptv). HO2 radicals in the range (2–3)×107 molecule cm−3 were observed at night. During NAMBLEX, a comprehensive suite of supporting measurements enabled a detailed study of the behaviour of HOx radicals under primarily clean marine conditions. Steady state expressions are used to calculate OH and HO2 concentrations and to evaluate the effect of different free-radical sources and sinks. The diurnally averaged calculated to measured OH ratio was 1.04±0.36, but the ratio displays a distinct diurnal variation, being less than 1 during the early morning and late afternoon/evening, and greater than 1 in the middle of the day. For HO2 there was an overprediction, with the agreement between calculated and measured concentrations improved by including reaction with measured IO and BrO radicals and uptake to aerosols. Increasing the concentration of IO radicals included in the calculations to above that measured by a DOAS instrument with an absorption path located mainly over the ocean, reflecting the domination of the inter-tidal region as an iodine source at Mace Head, led to further improvement. The results are compared with previous measurements at Mace Head, and elsewhere in the remote marine boundary layer.

The North Atlantic Marine Boundary Layer Experiment (NAMBLEX), involving over 50 scientists from 12 institutions, took place at Mace Head, Ireland (53.32° N, 9.90° W), between 23 July and 4 September 2002. A wide range of state-of-the-art instrumentation enabled detailed measurements of the boundary layer structure and atmospheric composition in the gas and aerosol phase to be made, providing one of the most comprehensive in situ studies of the marine boundary layer to date. This overview paper describes the aims of the NAMBLEX project in the context of previous field campaigns in the Marine Boundary Layer (MBL), the overall layout of the site, a summary of the instrumentation deployed, the temporal coverage of the measurement data, and the numerical models used to interpret the field data. Measurements of some trace species were made for the first time during the campaign, which was characterised by predominantly clean air of marine origin, but more polluted air with higher levels of NOx originating from continental regions was also experienced. This paper provides a summary of the meteorological measurements and Planetary Boundary Layer (PBL) structure measurements, presents time series of some of the longer-lived trace species (O3, CO, H2, DMS, CH4, NMHC, NOx, NOy, PAN) and summarises measurements of other species that are described in more detail in other papers within this special issue, namely oxygenated VOCs, HCHO, peroxides, organo-halogenated species, a range of shorter lived halogen species (I2, OIO, IO, BrO), NO3 radicals, photolysis frequencies, the free radicals OH, HO2 and (HO2+Σ RO2), as well as a summary of the aerosol measurements. NAMBLEX was supported by measurements made in the vicinity of Mace Head using the NERC Dornier-228 aircraft. Using ECMWF wind-fields, calculations were made of the air-mass trajectories arriving at Mace Head during NAMBLEX, and were analysed together with both meteorological and trace-gas measurements. In this paper a chemical climatology for the duration of the campaign is presented to interpret the distribution of air-mass origins and emission sources, and to provide a convenient framework of air-mass classification that is used by other papers in this issue for the interpretation of observed variability in levels of trace gases and aerosols.

No abstract available.