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This study explores our ability to simulate the atmospheric chemistry stemming from isoprene emissions in pristine and polluted regions of the Amazon basin. We confront two atmospheric chemistry models--a global, Eulerian chemistry-climate model (UM-UKCA) and a trajectory-based Lagrangian model (CiTTyCAT)--with recent airborne measurements of atmospheric composition above the Amazon made during the SAMBBA campaign of 2012. The simulations with the two models prove relatively insensitive to the chemical mechanism employed; we explore one based on the Mainz Isoprene Mechanism, and an updated one that includes changes to the chemistry of first generation isoprene nitrates (ISON) and the regeneration of hydroxyl radicals via the formation of hydroperoxy-aldehydes (HPALDS) from hydroperoxy radicals (ISO2). In the Lagrangian model, the impact of increasing the spatial resolution of trace gas emissions employed from 3.75° x 2.5° to 0.1° x 0.1° varies from one flight to another, and from one chemical species to another. What consistently proves highly influential on our simulations, however, is the model framework itself--how the treatment of transport, and consequently mixing, differs between the two models. The lack of explicit mixing in the Lagrangian model yields variability in atmospheric composition more reminiscent of that exhibited by the measurements. In contrast, the combination of explicit (and implicit) mixing in the Eulerian model removes much of this variability but yields better agreement with the measurements overall. We therefore explore a simple treatment of mixing in the Lagrangian model that, drawing on output from the Eulerian model, offers a compromise between the two models. We use this Lagrangian/Eulerian combination, in addition to the separate Eulerian and Lagrangian models, to simulate ozone at a site in the boundary layer downwind of Manaus, Brazil. The Lagrangian/Eulerian combination predicts a value for an AOT40-like accumulated exposure metric of around 1000 ppbv h, compared to just 20 ppbv h with the Eulerian model. The model framework therefore has considerable bearing on our understanding of the frequency at which, and the duration for which, the rainforest is exposed to damaging ground-level ozone concentrations. [ABSTRACT FROM AUTHOR]

Hydrocarbons are key precursors to two priority air pollutants, ozone and particulate matter. Those with two to seven carbons have historically been straightforward to observe and have been successfully reduced in many developed cities through air quality policy interventions. Longer chain hydrocarbons released from diesel vehicles are not considered explicitly as part of air quality strategies and there are few direct measurements of their gaseous abundance in the atmosphere. This study describes the chemically comprehensive and continuous measurements of organic compounds in a developed megacity (London), which demonstrate that on a seasonal median basis, diesel-related hydrocarbons represent only 20-30% of the total hydrocarbon mixing ratio but comprise more than 50% of the atmospheric hydrocarbon mass and are a dominant local source of secondary organic aerosols. This study shows for the first time that, 60% of the winter primary hydrocarbon hydroxyl radical reactivity is from diesel-related hydrocarbons and using the maximum incremental reactivity scale, we predict that they contribute up to 50% of the ozone production potential in London. Comparing real-world urban composition with regulatory emissions inventories in the UK and US highlights a previously unaccounted for but, very significant under-reporting of diesel related hydrocarbons; an underestimation of a factor ~ 4 for C9 species rising to a factor of over 70 for C12 during winter. These observations show that hydrocarbons from diesel vehicles can dominate gas phase reactive carbon in cities with high diesel fleet fractions. Future control of urban particulate matter and ozone in such locations requires a shift in policy focus onto gas phase hydrocarbons released from diesels as this vehicle type continues to displace gasoline world-wide. [ABSTRACT FROM AUTHOR]

Measurements of the radical species OH and HO2 were made using the Fluorescence Assay by Gas Expansion (FAGE) technique during a series of nighttime and daytime flights over the UK in summer 2010 and winter 2011. OH was not detected above the instrument's 1 o limit of detection during any of the nighttime flights or during the winter daytime flights, placing upper limits on [OH] of 1.8 x 106 molecule cm-3 and 6.4 x 105 molecule cm-3 for the summer and winter flights, respectively. HO2 reached a maximum concentration of 3.2 x 108 molecule cm-3 (13.6 pptv) during a nighttime flight on 20 July 2010, when the highest concentrations of NO3 and O3 were also recorded. Analysis of the rates of reaction of OH, O3, and the NO3 radical with measured alkenes indicates that the summer nighttime troposphere can be as important for the processing of VOCs as the winter daytime troposphere. 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 nighttime production of HO2 during summer, and reactions of O3 dominated nighttime HO2 production during winter. [ABSTRACT FROM AUTHOR]

Reaction with the hydroxyl radical (OH) is the dominant removal mechanism for virtually all volatile organic compounds (VOCs) in the atmosphere, however it can be difficult to reconcile measured OH reactivity with known sinks. Unresolved higher molecular weight VOCs contribute to OH sinks, of which monoaromatics are potentially an important sub-class. A method based on comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GCxGC-TOFMS) has been developed that extends the degree with which larger VOCs can be individually speciated from whole air samples (WAS). The technique showed excellent sensitivity, resolution and good agreement with an established GC-FID method, for compounds amenable to analysis on both instruments. Measurements have been made of VOCs within the UK east coast marine boundary layer and free troposphere, using samples collected from five aircraft flights in winter 2011. Ten monoaromatic compounds with an array of different alkyl ring substituents have been quantified, in addition to the simple aromatics, benzene, toluene, ethyl benzene and ∑m- and p-xylene. These additional compounds were then included into constrained box model simulations of atmospheric chemistry occurring at two UK rural and suburban field sites in order to assess the potential impact of these larger monoaromatics species on OH reactivity; they have been calculated to contribute an additional 2-6% to the overall modelled OH loss rate, providing a maximum additional OH sink of ~ 0.9 s-1. [ABSTRACT FROM AUTHOR]

We present an analysis of ozone photochemistry observed by aircraft measurements of boreal biomass burning plumes over Eastern Canada in the summer of 2011. Measurements of ozone and a number of key chemical species associated with ozone photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the quantifying the impact of BOReal forest fires on tropo-spheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS) experiment between 12 July and 3 August 2011. We found that ozone mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for ozone production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 15 days. Ozone production, calculated from ΔO3/ΔCO enhancement ratios, increased from 0.020 ± 0.008 ppbvppbv-1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbvppbv-1 in plumes with photochemical ages greater than 5 days. In comparing ozone mixing ratios with components of the NOy budget we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiencies of 8 ppbvppbv-1 relative to ΣAN and 2 ppbvppbv-1 relative to NOz. In plumes with ages greater than 4 days, ozone production efficiency increased to 473 ppbvppbv-1 relative to ΣAN and 155ppbvppbv-1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photosta-tionary steady state and ozone production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to ozone. The BORTAS measurements of ozone photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990. [ABSTRACT FROM AUTHOR]

Boreal forest fires are a significant source of chemicals to the atmosphere including numerous non-methane hydrocarbons (NMHCs). We report airborne measurements of NMHCs, acetone and methanol from >500 whole air samples collected over Eastern Canada, including interception of several different boreal biomass burning plumes. From these and concurrent measurements of carbon monoxide (CO) we derive fire emission ratios for 29 different species relative to the emission of CO. These range from 8.9±3.2 ppt ppb-1 CO for methanol to 0.007±0.004 ppt ppb-1 CO for cyclopentane. The ratios are in good to excellent agreement with recent literature values. Using the GEOS-Chem global 3-D chemical transport model (CTM) we show the influence of biomass burning on the global distributions of benzene, toluene, ethene and propene (species considered generally as indicative tracers of anthropogenic activity). Using our derived emission ratios and the GEOS-Chem CTM, we show that biomass burning can be the largest fractional contributor to observed benzene, toluene, ethene and propene in many global locations. The widespread biomass burning contribution to atmospheric benzene, a heavily regulated air pollutant, suggests that pragmatic approaches are needed when setting air quality targets as tailpipe and solvent emissions continue to decline. We subsequently determine the extent to which the 28 Global WMO-GAW stations worldwide are influenced by biomass burning sourced benzene, toluene, ethene and propene when compared to their exposure to anthropogenic emissions. [ABSTRACT FROM AUTHOR]

Measurements of total peroxy nitrates (ΣRO2NO2, ΣPNs), total alkyl nitrates (ΣRONO2, ΣANs) and nitrogen dioxide (NO2) were made above the surface of a Malaysian tropical rain forest in Borneo, using a laser-induced fluorescence instrument developed at the University of L'Aquila (Italy). This new instrument uses the direct excitation of NO2 at 532 nm in order to measure its concentrations detecting by the NO2 fluorescence at wavelengths longer than 610 nm. ΣPNs and ΣANs are indirectly measured after their thermal dissociation into NO2. Observations showed enhanced levels of NO2 during nighttime, an increase of ΣPNs during the afternoon and almost no evident diurnal cycle of ΣANs. The diurnal maximums of 200 pptv for ΣPNs and ΣANs are well below the peaks reported in other forest sites. A box model constrained with measured species, reproduces well the observed ΣPNs, but overestimates ΣANs concentrations. The reason of this model-observation discrepancy could be a wrong parameterization in the isoprene nitrates (INs) chemistry mechanism. Sensitivity tests show that: (1) reducing the yield of INs from the reaction of peroxy nitrates with NO to almost the lowest values reported in literature (5%), (2) reducing the INs recycling to 70% and (3) keeping the INs dry deposition at 4 cms-1 , improve the agreement between modelled and measured ΣANs of 20% on average. These results imply that in the tropical rain forest, even if ΣPNs and ΣANs concentrations are lower than those observed in other North American forests, the yield and dry deposition of INs are similar. Another comparable result is that in the INs oxidation its recycling dominates with only a 30% release of NO2, which has implications on tropospheric ozone production and aerosol budget. [ABSTRACT FROM AUTHOR]

The Emissions around the M25 motorway (EM25) campaign took place over the megacity of London in the United Kingdom in June 2009 with the aim of characterising trace gas and aerosol composition and properties entering and emitted from the urban region. It featured two mobile platforms, the UK BAe-146 Facility for Airborne Atmospheric Measurements (FAAM) research aircraft and a ground-based mobile lidar van, both travelling in circuits around London, roughly following the path of the M25 motorway circling the city. We present an overview of findings from the project, which took place during typical UK summertime pollution conditions. Emission ratios of volatile organic compounds (VOCs) emitted from the London region were consistent with measurements in and downwind of other large urban areas and indicated traffic and associated fuel evaporation were major sources. Sub-micron aerosol composition was dominated by secondary species including sulphate (24% of sub-micron mass in the London plume and 30% in the background aerosol), nitrate (24% plume; 18% background) and organic aerosol (30% plume; 30% background). The primary submicron aerosol emissions from London were minor compared to the larger regional background, with only limited increases in aerosol mass in the urban plume compared to the background (15% mass increase on average). Black carbon mass was the major exception, which more than doubled in the urban plume and lead to a decrease in the single scattering albedo from 0.91 in the background aerosol to 0.86 in the London plume, on average. Our observations indicated that regional aerosol appeared to dominate urban sources, at least during typical summertime conditions, meaning future efforts to reduce PM levels in London must account for regional as well as local aerosol sources. [ABSTRACT FROM AUTHOR]

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 x 106 molecule cm-3 (10min 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. [ABSTRACT FROM AUTHOR]

Biogenic volatile organic compounds (BVOCs) emitted from tropical rainforests comprise a substantial fraction of global atmospheric VOC emissions, however there are only relatively limited measurements of these species in tropical rainforest regions. We present observations of isoprene, α-pinene, camphene, Δ-3-carene, γ-terpinene and limonene, and oxygenated VOCs (OVOCs) of biogenic origin such as methacrolein, in ambient air above a tropical rainforest in Malaysian Borneo. Daytime composition was dominated by isoprene, with an average mixing ratio of the order of ∼1 ppb. γ-terpinene, limonene and camphene were the most abundant monoterpenes, with average daytime mixing ratios of 102, 71 and 66 ppt, respectively, and with an average monoterpene to isoprene ratio of 0.3 during sunlight hours, compared to 2.0 at night. Limonene and camphene abundances were seen to be related to both temperature and light conditions. In contrast, γ-terpinene emission occurred into the late afternoon/evening, under relatively low temperature and light conditions. We observe good agreement between surface and aircraft measurements of boundary layer isoprene and methacrolein above the natural rainforest, suggesting that the ground-level observations are broadly representative of isoprene emissions from this region. [ABSTRACT FROM AUTHOR]

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. 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. [ABSTRACT FROM AUTHOR]

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. Multi-variate 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. The largest contributors to the optimisation cost function at the point of best-fit are OH (41%), NO (18%) and total monoterpenes (16%). 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] 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 50-70% 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 FROM AUTHOR]

Pollutant plumes with enhanced levels of trace gases and aerosols were observed over the southern coast of West Africa during August 2006 as part of the AMMA wet season field campaign. Plumes were observed both in the mid and upper troposphere. In this study we examined both the origin of these pollutant plumes and their potential to produce O3 downwind over the Atlantic Ocean. Runs using the BOLAM mesoscale model including biomass burning CO tracers were used to confirm an origin from central African fires. The plumes in the mid troposphere had significantly higher pollutant concentrations due to the fact that transport occurred from a region nearer or even over the fire region. In contrast, plumes transported into the upper troposphere over West Africa had been transported to the north-east of the fire region before being uplifted. Modelled tracer results showed that pollutants resided for between 9 and 12 days over Central Africa before being transported for 4 days, in the case of the mid-troposphere plume and 2 days in the case of the upper tropospheric plume to the measurement location over the southern part of West Africa. Around 35% of the biomass burning tracer was transported into the upper troposphere compared to that remaining in the mid troposphere. Runs using a photochemical trajectory model, CiTTyCAT, were used to estimate the net photochemical O3 production potential of these plumes. The mid tropospheric plume was still very photochemically active (up to 7 ppbv/day) especially during the first few days of transport westward over the Atlantic Ocean. The upper tropospheric plume was also still photochemically active, although at a slower rate (1-2 ppbv/day). Trajectories show this plume being recirculated around an upper tropospheric anticyclone back towards the African continent (around 20°S). The potential of theses plumes to produce O3 supports the hypothesis that biomass burning population are contributing to the observed O3 maxima over the southern Atlantic at this time of year. [ABSTRACT FROM AUTHOR]

Concentrations and fluxes of eight volatile organic compounds (VOCs) were measured during October 2006 from a high telecom tower above central London, as part of the CityFlux contribution to the REPARTEE I campaign. A continuous flow disjunct eddy covariance technique with analysis by proton transfer reaction mass spectrometry was used. Daily averaged VOC mixing ratios were within the range 1-19 ppb for the oxygenated compounds (methanol, acetaldehyde and acetone) and 0.2-1.3 ppb for the aromatics (benzene, toluene and ethylbenzene). Typical VOC fluxes were in the range 0.1-1.0mgm-2 h-1. There was a non-linear relationship between VOC fluxes and traffic density for most of the measured compounds. Traffic activity was estimated to account for approximately 70% of the aromatic compound fluxes, whereas non-traffic related sources were found to be more important for methanol and isoprene fluxes. The measured fluxes were comparable to the estimates of the UK national atmospheric emission inventory for the aromatic VOCs and CO. In contrast, fluxes of the oxygenated compounds were about three times larger than inventory estimates. For isoprene and acetonitrile this difference was many times larger. At temperatures over 25°C it is estimated that more than half the isoprene observed in central London is of biogenic origin. [ABSTRACT FROM AUTHOR]

We report here top-down emissions estimate for an African megacity. A boundary-layer circumnavigation of Lagos, Nigeria was completed using the FAAM BAe146 aircraft as part of the AMMA project. These observations together with an inferred boundary-layer 5 height allow the flux of pollutants to be calculated. Extrapolation gives annual emissions for CO, NOx and VOCs of 0.72 TgCyr-1, 0.02 TgNyr-1 and 0.28 TgCyr-1 respectively, consistent with bottom-up estimates for other developing megacities. These emissions are attributed to the evaporation of fuels, mobile combustion and natural gas emissions. [ABSTRACT FROM AUTHOR]

This paper presents measurements of organic aerosols above subtropical West Africa during the wet season using data from the UK Facility for Airborne Atmospheric Measurements (FAAM) aircraft. Measurements of biogenic volatile organic compounds (BVOC) at low altitudes over these subtropical forests were made during the African Monsoon Multidisciplinary Analysis (AMMA) field experiment during July and August 2006 mainly above Benin, Nigeria and Niger. Data from an Aerodyne Quadrupole Aerosol Mass Spectrometer show a median organic aerosol loading of 1.08 μg m-3 over tropical West Africa, which represents the first regionally averaged assessment of organic aerosol mass (OM) in this region during the wet season. This is in good agreement with predictions based on aerosol yields from isoprene and monoterpenes during chamber studies and model predictions based on partitioning schemes, contrasting markedly with the large under representations of OM in similar models when compared with data from mid latitudes. [ABSTRACT FROM AUTHOR]

The distribution of trace gases upwind and above the Mace Head Atmospheric Research Station, Ireland has been determined using measurements made from aircraft. The observations indicate excellent agreement between most non-methane hydrocarbons, dimethyl sulphide (DMS) and ozone measured at the surface, at 390m overhead and in upwind boundary layer regions of the coastal Atlantic. Vertical profiles above the observatory indicated that local convective events result in a marine influence being detected at 3 km and above. The observation of isoprene from maritime sources at these levels was indicative of very rapid uplift on the hour timescale. Measurements of trace gases were also made directly upwind of the observatory over coastal regions and as far as the deep open ocean beyond the continental shelf. A maximum of 240 pptV DMS was observed in the boundary layer near to the shelf region, declining to a concentration of around 40 pptV at the coastline. The upwelling of nutrient rich waters at the ocean shelf location may be a possible explanation for the high abundance of DMS in these regions. The observations suggest that this region, some 150-200 km from the observatory, would under these environmental conditions have a major influence in the determining the DMS observed on-shore. The spatial distribution of ethene within boundary layer over coastal and deep waters differed significantly from DMS with an almost uniform abundance over all ocean regions. [ABSTRACT FROM AUTHOR]

Several zero-dimensional box-models with different levels of chemical complexity, based on the Master Chemical Mechanism (MCM), have been used to study the chemistry of OH and HO2 in a coastal environment in the Northern Hemisphere. The models were constrained to and compared with measurements made during the NAMBLEX campaign (Mace Head, Ireland) in summer 2002. The base models, which were constrained to measured CO, CH4 and NMHCs, were able to reproduce [OH] within 25%, but overestimated [HO2] by about a factor of 2. Agreement was improved when the models were constrained to oxygenated compounds (acetaldehyde, methanol and acetone), highlighting their importance for the radical budget. When the models were constrained to measured halogen monoxides (IO, BrO) and used a more detailed, measurements-based, treatment to describe the heterogeneous uptake, modelled [OH] increased by up to 15% and [HO2] decreased by up to 30%. The actual impact of halogen monoxides on the modelled concentrations of HOx was dependant on the uptake coefficients used for HOI, HOBr and HO2. The best agreement with the measurements was achieved by constraining the model to measured IO and setting γHO2 = 1 and γHOI = 0.6. A rate of production and destruction analysis of the models allowed a detailed study of OH and HO2 chemistry under the conditions encountered during NAMBLEX, showing the importance of oxygenates and of XO (where X=I, Br) as co-reactants for OH and HO2 and of HOX photolysis as a source for OH. [ABSTRACT FROM AUTHOR]

Measurements of acetone, methanol, acetaldehyde and a range of non-methane hydrocarbons have been made in North Atlantic marine air at the Mace Head observatory. Under maritime conditions the combination of OVOCs (acetone, methanol and acetaldehyde) contributed up to 85% of the total mass of measured non methane organics in air and up to 80% of the OH radical organic sink, when compared with the sum of all other organic compounds including non-methane hydrocarbons, DMS and OH-reactive halocarbons (trichloromethane and tetrachloroethylene). The observations showed anomalies in the variance and abundance of acetaldehyde and acetone over that expected for species with a remote terrestrial emission source and OH controlled chemical lifetime. A detailed model incorporating an explicit chemical degradation mechanism indicated in situ formation during air mass transport was on timescales longer than the atmospheric lifetime of precursor hydrocarbons or primary emission. The period over which this process was significant was similar to that of airmass motion on intercontinental scales, and formation via this route may reproduce that of a widespread diffuse source. The model indicates that continued short chain OVOC formation occurs many days from the point of emission, via longer lived intermediates of oxidation such as organic peroxides and long chain alcohols. [ABSTRACT FROM AUTHOR]