Street-level concentrations of nitrogen dioxide (NO(2)) and particulate matter (PM) exceed public health standards in many cities, causing increased mortality and morbidity. Concentrations can be reduced by controlling emissions, increasing dispersion, or increasing deposition rates, but little attention has been paid to the latter as a pollution control method. Both NO(2) and PM are deposited onto surfaces at rates that vary according to the nature of the surface; deposition rates to vegetation are much higher than those to hard, built surfaces. Previously, city-scale studies have suggested that deposition to vegetation can make a very modest improvement (<5%) to urban air quality. However, few studies take full account of the interplay between urban form and vegetation, specifically the enhanced residence time of air in street canyons. This study shows that increasing deposition by the planting of vegetation in street canyons can reduce street-level concentrations in those canyons by as much as 40% for NO(2) and 60% for PM. Substantial street-level air quality improvements can be gained through action at the scale of a single street canyon or across city-sized areas of canyons. Moreover, vegetation will continue to offer benefits in the reduction of pollution even if the traffic source is removed from city centers. Thus, judicious use of vegetation can create an efficient urban pollutant filter, yielding rapid and sustained improvements in street-level air quality in dense urban areas.

Abstract. Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multivariate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%), NO (22%) and total peroxy radicals (27%). Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR) and methyl-vinyl ketone (MVK) are substantially overestimated, and the hydroxyl radical (OH)Correspondence to: T. A. M. Pugh (t.pugh@lancs.ac.uk) concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs). Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with increased deposition of intermediates and some modest OH recycling, is able to produce both isoprene and OH concentrations within error of those measured. Whilst we cannot rule out an important role for missing chemistry, particularly in areas of higher isoprene flux, this study demonstrates that the inadequacies apparent in box and global model studies of tropical VOC chemistry may be more strongly influenced by representation of detailed physical and micrometeorological effects than errors in the chemical scheme.

Abstract. As part of the OP3 field study of rainforest atmospheric chemistry, above-canopy fluxes of isoprene, monoterpenes and oxygenated volatile organic compounds were made by virtual disjunct eddy covariance from a SouthEast Asian tropical rainforest in Malaysia. Approximately 500 hours of flux data were collected over 48 days in AprilMay and June-July 2008. Isoprene was the dominant nonmethane hydrocarbon emitted from the forest, accounting for 80% (as carbon) of the measured emission of reactive carbon fluxes. Total monoterpene emissions accounted for 18% of the measured reactive carbon flux. There was no evidence for nocturnal monoterpene emissions and during the day their flux rate was dependent on both light and temperature. The oxygenated compounds, including methanol, acetone and acetaldehyde, contributed less than 2% of the total measured reactive carbon flux. The sum of the VOC fluxes measured represents a 0.4% loss of daytime assimilated carbon by the canopy, but atmospheric chemistry box modelling suggests that most (90%) of this reactive carbon is returned back to the canopy by wet and dry deposition following chemical transformation. The emission rates of isoprene and monoterpenes, normalised to 30 • C and 1000 µmol m −2 s −1 PAR, were 1.6 mg m −2 h −1 and 0.46 mg m −2 h −1 respectively, which was 4 and 1.8 times lower respectively than the default value for tropical forests in the widely-used MEGAN Correspondence to: B. Langford (b.langford1@lancaster.ac.uk) model of biogenic VOC emissions. This highlights the need for more direct canopy-scale flux measurements of VOCs from the world's tropical forests.

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. We quantify the sensitivity to mixing of chlorine deactivation and ozone depletion in simplified models of the northern hemisphere, middle-latitude lower stratosphere. A photochemical box model augmented by a volume exchange model of mixing was used to identify situations for which effects of C1Ox deactivation through mixing with NOx-rich air are at least as important as photochemical effects alone. In one simulation representative of a filament of high-latitude, C1Ox-activated air mixing with low-latitude air, the O• depletion rate was found to be 0.287%, 0.127%, or 0.08% day -1, for a volume exchange rate of 0, 0.06, or 0.48 day -1, respectively. If we take the first rate as representative of Lagrangian models, the second rate as typical of the lower stratosphere, and the third rate as typical of those grid-based models that do not resolve the real mixing length scales, then our results suggest that Lagrangian models that do not represent mixing processes can, in certain circumstances, be in error by as much or more than grid-based models. The box model results allowed the formulation of a simplified, yet reasonably accurate reaction scheme for mixing-induced chlorine deactivation which was then implemented in a two-dimensional model of quasi-horizontal transport along isentropic surfaces. The two-dimensional model represents mixing by an effective horizontal diffusivity that accounts for vertical diffusivity and horizontal strain, and for advective transport it uses winds from lower stratospheric observational analyses. Mixing-induced chlorine deactivation was found to exhibit substantial sensitivity to the effective diffusivity of the two-dimensional model.

This is a repository copy of Enhanced global primary production by biogenic aerosol via diffuse radiation fertilization.

This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs) from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS), measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 %) of all emitted BVOCs measured, at up to 30 mg m⁻² h⁻¹ over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) exhibited clear deposition of 1 mg m⁻² h⁻¹, with a small average canopy resistance of 230 s m⁻¹. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m⁻² h⁻¹, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m⁻² h⁻¹ was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010), we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions

Abstract. An aircraft measurement campaign involving the Russian high-altitude aircraft M55 Geophysica and the German DLR Falcon was conducted in Darwin, Australia in November and December 2005 as part of the European integrated project SCOUT-O3. The overall objectives of the campaign were to study the transport of trace gases through the tropical tropopause layer (TTL), mechanisms of dehydration close to the tropopause, and the role of deep convection in these processes. In this paper a detailed roadmap of the campaign is presented, including rationales for each flight, and an analysis of the local and large-scale meteorological context in which they were embedded. The campaign took place during the pre-monsoon season which is characterized by a pronounced diurnal evolution of deep convection including a mesoscale system over the Tiwi Islands north of Darwin known as "Hector". This allowed studying in detail the role of deep convection in structuring the tropical tropopause region, in situ sampling convective overshoots above storm anvils, and probing the structure of anvils and cirrus clouds by Lidar and a suite of in situ instruments onboard the two aircraft. The large-scale flow during the first half of the campaign was such that local flights, away from convection, samCorrespondence to: D. Brunner (dominik.brunner@empa.ch) pled air masses downstream of the "cold trap" region over Indonesia. Abundant cirrus clouds enabled the study of active dehydration, in particular during two TTL survey flights. The campaign period also encompassed a Rossby wave breaking event transporting stratospheric air to the tropical middle troposphere and an equatorial Kelvin wave modulating tropopause temperatures and hence the conditions for dehydration.