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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 (NO3 x = 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 per-oxy 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. [ABSTRACT FROM AUTHOR]

The RONOCO 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 measurement of these species. We compare the observed concentrations of these short-lived species with those cal-culated 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 the model predictions. The model systematically underpredicts HO2 by a factor of ∼ 2 and overpredicts NO3 and N2O5 by factors of around 75% 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 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 oxidation chain. Model sensitivity to the N2O5 aerosol uptake co-efficient (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, howeverthe nature of these compounds is extremely uncertain. [ABSTRACT FROM AUTHOR]

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I). The input of marine halogens to the stratosphere is based on observations and modeling studies using low resolution oceanic emission scenarios derived from top down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1° x 1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 GmolBryr-1 for CHBr3, 0.78/0.98 GmolBryr-1 for CH2Br2 and 1.24/1.45 GmolI yr-1 for CH3I (Robust Fit/Ordinary Least Square regression technique). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic region. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An underrepresentation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom up emission estimate and top down approaches. [ABSTRACT FROM AUTHOR]

The atmospheric records of four halons, H-1211 (CBrClF2), H-1301 (CBrF3), H-2402 (CBrF2CBrF2) and H-1202 (CBr2F2), measured from air collected at Cape Grim, Tasmania between 1978 and 2011, are reported. Mixing ratios of H-1211, H-2402 and H1202 began to decline in the early to mid-2000s but those of H-1301 continue to increase throughout the record. These trends are compared to those reported by NOAA (National Oceanic and Atmospheric Administration) and AGAGE (Advanced Global Atmospheric Experiment). The continued increase of H-1301 mixing ratios means that the contribution of the halons to total tropospheric bromine is not declining. Top-down global annual emissions of the halons were derived using a two-dimensional atmospheric model. The emissions of all four have decreased since peaking in the late 1980s-mid 1990s but this decline has slowed recently, particularly for H-1301 and H2402 which have shown no decrease in emissions over the past five years. The UEA top-down model derived emissions are compared to those reported using a top-down approach by NOAA and AGAGE and the bottom-up estimates of HTOC (Halons Technical Options Committee). Additionally results are presented that suggest that H-1202 emissions are linked to H-1211 emissions rather than H-1211 production. Finally revised steady state atmospheric lifetimes are reported as 14yrfor H-1211, 75yrfor H1301, 17yr for H-2402 and 2.6 yr for H-1202. These revised lifetimes would reduce the estimated existing bank of H-1211 by over 80% to 10Gg while increasing the H-1301 bank by 15%to49Gg. [ABSTRACT FROM AUTHOR]

We use 2005-2009 satellite observations of formaldehyde (HCHO) columns from OMI to infer biogenic isoprene emissions at monthly 1 x1° resolution over the African continent. Our work includes new approaches to remove biomass burning influences using OMI absorbing aerosol optical depth data (to account for transport of fire plumes) and anthropogenic influences using AATSR satellite data for persistent small-flame fires (gas flaring). The resulting biogenic HCHO columns (ΩHCHO) follow closely the distribution of vegetation patterns in Africa. We infer isoprene emission (EISOP ) from the local sensitivity S = ΔΩ HCHO /ΔEISOP derived with the GEOS-Chem chemical transport model using two alternate isoprene oxidation mechanisms, and verify the validity of this approach using AMMA aircraft observations over West Africa and a longitudinal transect across central Africa. Displacement error (smearing) is diagnosed by anomalously high values of S and the corresponding data are removed. We find significant sensitivity of S to NOx under low-NOx conditions that we fit to a linear function of tropospheric column NO2 from OMI. We estimate a 40% error in our inferred isoprene emissions under high-NO2 conditions and 40-90% under low-NOx conditions. Comparison to the state-of-science MEGAN inventory indicates a large overestimate of central African rainforest emissions in that inventory. [ABSTRACT FROM AUTHOR]

We report the first data set of atmospheric abundances for the following four perfluoroalkanes: n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetra-decafluorohexane (n-C6F14) and n-hexadecafluoroheptane (n-C7F16). All four compounds could be detected and quantified in air samples from remote locations in the Southern Hemisphere (at Cape Grim, Tasmania, archived samples dating back to 1978) and the upper troposphere (a passenger aircraft flying from Germany to South Africa). Further observations originate from air samples extracted from deep firn in Greenland and allow trends of atmospheric abundances in the earlier 20th century to be inferred. All four compounds were not present in the atmosphere prior to the 1960s. n-C4F10 and n-C5F12 were also measured in samples collected in the stratosphere confirming their very long atmospheric lifetimes. Emissions were inferred from these observations and found to be comparable with emissions from the EDGAR database for n-C6F14. However, emissions of n-C4F10, n-C5F12 and n-C7F16 were found to differ by up to five orders of magnitude. Although the abundances of the four perfluorocarbons reported here are currently small (less than 0.3 ppt, parts per trillion) they have strong Global Warming Potentials several thousand times higher than carbon dioxide and continue to increase in the atmosphere. The sum of their cumulative emissions reached 325mt (million metric tonnes) CO2 equivalent at the end of 2009. [ABSTRACT FROM AUTHOR]

Long term measurements in background air (Cape Grim, Tasmania) and firn air (NEEM, Greenland) of the "super" greenhouse gas SF5CF3 show that emissions declined after the late 1990s, having grown since the 1950s, and became indistinguishable from zero after 2003. It is concluded that this is due to the cessation of global production of perfluorooctyl sulfonate-based fluorochemicals. An earlier observation of closely correlated atmospheric abundances of SF5CF3 and SF6 are shown here to have likely been purely coincidental, as their respective trends diverged after 2002. Due to its long lifetime (ca. 900 yr), atmospheric concentrations of SF5CF3 have not declined, and it is now well mixed between hemispheres, as is also shown here from interhemispheric aircraft measurements. Total cumulative emissions of SF5CF3 amount to around 5 kT. [ABSTRACT FROM AUTHOR]

Air samples collected at Cape Grim, Tasmania between 1978 and 2008 and during a series of more recent aircraft sampling programmes have been analysed to determine the atmospheric abundance and trend of octafluorocyclobutane (c-C4F8 or PFC- 318). c-C4F8 has an atmospheric lifetime in excess of 3000 yr and a global warming potential (GWP) of 10 300 (100 yr time horizon), making it one of the most potent greenhouse gases detected in the atmosphere to date. The abundance of c-C4F8 in the Southern Hemisphere has risen from 0.35 ppt in 1978 to 1.2 ppt in 2010, and is currently increasing at a rate of around 0.03 ppt yr-1. It is the third most abundant perfluorocarbon (PFC) in the present day atmosphere, behind CF4 (~ 75 ppt) and C2F6 (~ ppt). The origin of c-C4F8 is unclear. Using a 2-D global model to derive top-down global emissions based on the Cape Grim measurements yields a recent (2007) emission rate of around 1.1Gg yr-1 and a cumulative emission up to and including 2007 of 38.1 Gg. Emissions reported on the EDGAR emissions database for the period 1986- 2005 represent less than 1% of the top-down emissions for the same period, which suggests there is a large unaccounted for source of this compound. It is also apparent that the magnitude of this source has varied considerably over the past 30 yr, declining sharply in the late 1980s before increasing again in the mid-1990s. [ABSTRACT FROM AUTHOR]

Atmospheric composition affects the radiative balance of the Earth through the creation of greenhouse gases and the formation of aerosols. The latter interact with incoming solar radiation, both directly and indirectly through their effects on cloud formation and lifetime. The tropics have a major influence on incoming sunlight however the tropical atmosphere is poorly characterised, especially outside Amazonia. The origins of air masses influencing a measurement site in a protected rainforest in Borneo, South East Asia, were assessed and the likely sources of a range of trace gases and particles were determined. This was conducted by interpreting in situ measurements made at the site in the context of ECMWF backwards air mass trajectories. Two different but complementary methods were employed to interpret the data: comparison of periods classified by cluster analysis of trajectories, and inspection of the dependence of mean measured values on geographical history of trajectories. Sources of aerosol particles, carbon monoxide and halocarbons were assessed. The likely source influences include: terrestrial organic biogenic emissions; long range transport of anthropogenic emissions; biomass burning; sulphurous emissions from marine phytoplankton, with a possible contribution from volcanoes; marine production of inorganic mineral aerosol; and marine production of halocarbons. Aerosol sub- and super-saturated water affinity was found to be dependent on source (and therefore composition), with more hygroscopic aerosol and higher numbers of cloud condensation nuclei measured in air masses of marine origin. The prevailing sector during the majority of measurements was south-easterly, which is from the direction of the coast closest to the site, with a significant influence inland from the south-west. This analysis shows that marine and terrestrial air masses have different dominant chemical sources. Comparison with the AMAZE-08 project in the Amazon basin shows Bornean composition to arise from a different, more complex mixture of sources. In particular sulphate loadings are much greater than in Amazonia which is likely to mainly be the result of the marine influence on the site. This suggests that the significant region of the tropics made up of island networks is not well represented by extrapolation from measurements made in the Amazon. In addition, it is likely that there were no periods where the site was influenced only by the rainforest, with even the most pristine inland periods showing some evidence of non-rainforest aerosol. This is in contrast to Amazonia which experienced periods dominated by rainforest emissions. [ABSTRACT FROM AUTHOR]

A global chemistry-climate model LMDz INCA is used to investigate the contribution of African and Asian emissions to tropospheric ozone over central and West Africa during the summer monsoon. The model results show that ozone in this region is most sensitive to lightning NOx and to central African biomass burning emissions. However, other emission categories also contribute significantly to regional ozone. The maximum ozone changes due to lightning NOx occur in the upper troposphere between 400 hPa and 200 hPa over West Africa and downwind over the Atlantic Ocean. Biomass burning emissions mainly influence ozone in the lower and middle troposphere over central Africa, and downwind due to westward transport. Biogenic emissions of volatile organic compounds, which can be uplifted from the lower troposphere into higher altitudes by the deep convection that occurs over West Africa during the monsoon season, dominate the ozone changes in the upper troposphere and lower stratosphere region. Convective uplift of soil NOx emissions over the Sahel region also makes a significant contribution to ozone in the upper troposphere. Concerning African anthropogenic emissions, they make a lower contribution to ozone compared to the other emission categories. The model results indicate that most ozone changes due to African emissions occur downwind, especially over the Atlantic Ocean, far from the emission regions. The influence of Asian emissions should also be taken into account in studies of the ozone budget over Africa since they make a considerable contribution to ozone concentrations above 150 hPa. Using IPCC AR5 (Intergovernmental Panel on Climate Change; Fifth Assessment Report) estimates of anthropogenic emissions for 2030 over Africa and Asia, the model calculations suggest largest changes in ozone due to the growth of emissions over Asia than over Africa over the next 20 years. [ABSTRACT FROM AUTHOR]

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 Due to image rights restrictions. and 1.Due to image rights restrictions. 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. [ABSTRACT FROM AUTHOR]

OH and HO2 aircraft 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) 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. [ABSTRACT FROM AUTHOR]

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+∑RO2, 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. [ABSTRACT FROM AUTHOR]

We report the first measurements of 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), a substitute for ozone depleting compounds, in remote regions of the atmosphere and present evidence for its rapid growth. Observed mixing ratios ranged from below 0.01 ppt in deep firn air to 0.59 ppt in the northern mid-latitudinal upper troposphere. Firn air samples collected in Greenland were used to reconstruct a history of atmospheric abundance. Year-on-year increases were deduced, with acceleration in the growth rate from 0.026 ppt per year in 2000 to 0.057 ppt per year in 2007. Upper tropospheric air samples provide evidence for a continuing growth until late 2009. Furthermore we calculated a stratospheric lifetime of 370 years from measurements of air samples collected on board high altitude aircraft and balloons. Emission estimates were determined from the reconstructed atmospheric trend and suggest that current "bottom-up" estimates of global emissions for 2005 are too high by more than a factor of three. [ABSTRACT FROM AUTHOR]

We have performed simulations using a 3-D global chemistry-transport model (TM4 AMMA) to investigate the effect that continental transport of biomass burning plumes have on regional air quality over Equatorial Africa during the West African Monsoon (WAM) period in 2006. By performing a number of sensitivity studies we show that biomass burning emissions from southern Africa (0-40° S) have a strong influence on the composition of the tropical troposphere around Equatorial Africa and the outflow regions towards the west, especially between 10° S-10° N. By altering both the temporal distribution and the injection heights used for introducing the biomass burning emissions we show that changes in temporal distribution are much more important in determining the daily variability of trace gas species over the southern Atlantic than boundary layer processes. When adopting the GFEDv2 emission inventory the maximum concentrations in CO and O3 occur between 0-5° S, which coincides with the position of the southern African Easterly Jet. By comparing co-located model output with in-situ measurements made during the AMMA measurement campaign we show that the model fails to capture the tropospheric profile of CO in the burning region, as well as the "extreme" concentrations of both CO and O3 seen around 600-700 hPa above Equatorial Africa. Trajectory analysis show that the 6-hourly ECMWF meteorological fields do not allow transport of biomass burning plumes from southern Africa directly into the mid-troposphere around ∼6° N. Similar trajectory simulations repeated using an updated meteorological dataset, which assimilates additional measurement data for the African region, shows markedly different origins for pollution events and reveals that the performance of the CTM is heavily constrained by the ECMWF operational analysis data which drives the model. [ABSTRACT FROM AUTHOR]

During June, July and August 2006 five aircraft took part in a campaign overWest Africa to observe the aerosol content and chemical composition of the troposphere and lower stratosphere as part of the African Monsoon Multidisciplinary Analysis (AMMA) project. These are the first such measurements in this region during the monsoon period. In addition to providing an overview of the tropospheric composition, this paper provides a description of the measurement strategy (flights performed, instrumental payloads, wing-tip to wing-tip comparisons) and points to some of the important findings discussed in more detailed in other papers in this special issue. The ozone data exhibits an "S" shaped vertical profile which appears to result from significant losses in the lower troposphere due to rapid deposition to forested areas and photochemical destruction in the moist monsoon air, and convective uplift of O3-poor air to the upper troposphere. This profile is disturbed, particularly in the south of the region, by the intrusions in the lower and middle troposphere of air from the Southern Hemisphere impacted by biomass burning. Comparisons with longer term data sets suggest the impact of these intrusions on West Africa in 2006 was greater than in other recent wet seasons. There is evidence for net photochemical production of ozone in these biomass burning plumes as well as in urban plumes, in particular that from Lagos, convective outflow in the upper troposphere and in boundary layer air affected by nitrogen oxide emissions from recently wetted soils. This latter effect, along with enhanced deposition to the forested areas, contributes to a latitudinal gradient of ozone in the lower troposphere. Biogenic volatile organic compounds are also important in defining the composition both for the boundary layer and upper tropospheric convective outflow. Mineral dust was found to be the most abundant and ubiquitous aerosol type in the atmosphere over Western Africa. Data collected within AMMA indicate that injection of dust to altitudes favourable for long-range transport (i.e. in the upper Sahelian planetary boundary layer) can occur behind the leading edge of mesoscale convective system (MCS) cold-pools. Research within AMMA also provides the first estimates of secondary organic aerosols (SOA) across the West African Sahel and have shown that organic mass loadings vary between 0 and 2 μgm-3 with a median concentration of 1.07 μgm-3. The vertical distribution of nucleation mode particle concentrations reveals that significant and fairly strong particle formation events did occur for a considerable fraction of measurement time above 8km (and only there). Very low aerosol concentrations were observed in general in the fresh outflow of active MCSs, likely as the result of efficient wet removal of aerosol particles due to heavy precipitation inside the convective cells of the MCSs. This wet removal initially affects all particle size ranges as clearly shown by all measurements in the vicinity of MCSs. [ABSTRACT FROM AUTHOR]

Isoprene emissions are the largest source of reactive carbon to the atmosphere, with the tropics being a major source region. These natural emissions are expected to change with changing climate and human impact on land use. As part of the African Monsoon Multidisciplinary Analyses (AMMA) project the Model of Emissions of Gases and Aerosols from Nature (MEGAN) has been used to estimate the spatial and temporal distribution of isoprene emissions over the West African region. During the AMMA field campaign, carried out in July and August 2006, isoprene mixing ratios were measured on board the FAAM BAe-146 aircraft. These data have been used to evaluate the model performance. MEGAN was firstly applied to a large area covering much of West Africa from the Gulf of Guinea in the south to the desert in the north and was able to capture the large scale spatial distribution of isoprene emissions as inferred from the observed isoprene mixing ratios. In particular the model captures the transition from the forested area in the south to the bare soils in the north, but some discrepancies have been identified over the bare soil, mainly due to the emission factors used. Sensitivity analyses were performed to assess the model response to changes in driving parameters, namely Leaf Area Index (LAI), Emission Factors (EF), temperature and solar radiation. A high resolution simulation was made of a limited area south of Niamey, Niger, 20 where the higher concentrations of isoprene were observed. This is used to evaluate the model's ability to simulate smaller scale spatial features and to examine the influence of the driving parameters on an hourly basis through a case study of a flight on 17 August 2006. This study highlights the complex interactions between land surface processes and the meteorological dynamics and chemical composition of the PBL. This has implications for quantifying the impact of biogenic emissions on the atmospheric composition over West Africa and any changes that may occur with changing climate. [ABSTRACT FROM AUTHOR]

In this paper we describe measurements of volatile organic compounds (VOCs) made using a Proton Transfer Reaction Mass Spectrometer (PTR-MS) aboard the UK Facility for Atmospheric Airborne Measurements during the African Monsoon Multidisciplinary Analyses (AMMA) campaign. Observations were made during approximately 85 h of flying time between 17 July and 17 August 2006, above an area between 4° N and 18° N and 3°W and 4° E, encompassing ocean, mosaic forest, and the Sahel desert. High time resolution observations of counts at mass to charge (m/z) ratios of 42, 59, 69, 71, and 79 were used to calculate mixing ratios of acetonitrile, acetone, isoprene, the sum of methyl vinyl ketone and methacrolein, and benzene, respectively using laboratory-derived humidity-dependent calibration factors. Strong spatial associations between vegetation and isoprene and its oxidation products were observed in the boundary layer, consistent with biogenic emissions followed by rapid atmospheric oxidation. Acetonitrile, benzene, and acetone were all enhanced in airmasses which had been heavily influenced by biomass burning. Benzene and acetone were also elevated in airmasses with urban influence from cities such as Lagos, Cotonou, and Niamey. The observations provide evidence that both deep convection and mixing associated with fair-weather cumulus were responsible for vertical redistribution of VOCs emitted from the surface. Profiles over the ocean showed a depletion of acetone in the marine boundary layer, but no significant decrease for acetonitrile. [ABSTRACT FROM AUTHOR]

As part of the African Monsoon Multidisciplinary Analysis (AMMA) program, a total of 98 ozone vertical profiles over Cotonou, Benin, have been measured during a 26 month period (December 2004-January 2007). These regular measurements broadly document the seasonal and inter annual variability of ozone in both the troposphere and the lower stratosphere over West Africa for the first time. This data set is complementary to the MOZAIC observations made from Lagos between 0 and 12 km during the period 1998-2004. Both data sets highlight the unique way in which West Africa is impacted by two biomass burning seasons: in December-February (dry season) due to burning in the Sahelian band and in June-August (wet season) due to burning in southern Africa. High inter annual variabilities between Cotonou and Lagos data sets and within each data set are observed and are found to be a major characteristic of this region. In particular, the dry and wet seasons are discussed in order to set the data of the Special Observing Periods (SOPs) into a climatological context. Compared to other dry and wet seasons, the dry and wet season campaigns took place in rather high ozoneenvironments. During the sampled wet seasons, southern intrusions of biomass burning were particularly frequent with concentrations up to 120 ppbv of ozone in the lower troposphere. An insight into the ozone distribution in the upper troposphere and the lower stratosphere (up to 26 km) is given. The first tropospheric columns of ozone based on in-situ data in this region are assessed. They compare well with satellite products on seasonal and inter annual time-scales, provided that the layer below 850 hPa where the remote instrument is less sensitive to ozone, is removed. [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]

A bi-dimensional latitudinal-vertical meterological model coupled with O3-NOx-VOC chemistry is used to reproduce the distribution of ozone and precursors in the boundary layer over West Africa during the African Monsoon Multidisciplinary Analysis (AMMA) 5 campaign as observed on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft. The model reproduces the increase of ozone mixing ratios in the boundary layer observed between the forested region south of 13° N and the Sahelian area northward. Sensitivity and budget analysis reveals that the intertropical convergence zone is a moderate source of O3 rich-air in the boundary layer due to convective downdrafts. Dry deposition drives the ozone minimum over the vegetated area. The combination of high NOx emissions from soil north of 13° N and northward advection by the monsoon flux of VOC-enriched air masses contributes to the ozone maximum simulated at higher latitudes. Simulated OH exhibit a well marked latitudinal gradient with minimum concentrations over the vegetated 15 region where the reactions with biogenic compounds predominate. The model underestimates the observed OH mixing ratios, however this model discrepancy has slight effect on ozone budget and does not alter the conclusions. [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]

Chemical and meteorological parameters measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the African Monsoon Multidisciplinary Analysis (AMMA) campaign are presented to show the impact of NOx emissions from recently wetted soils in West Africa. NOx emissions from soils have been previously observed in many geographical areas with different types of soil/vegetation cover during small scale studies and have been inferred at large scales from satellite measurements of NOx. This study is the first dedicated to showing the emissions of NOx at an intermediate scale between local surface sites and continental satellite measurements. The measurements reveal pronounced mesoscale variations in NOx concentrations closely linked to spatial patterns of antecedent rainfall. Fluxes required to maintain the NOx concentrations observed by the BAe-146 in a number of cases studies and for a range of assumed OH concentrations (0 to 1 x 107 molecules cm-3) are calculated to be in the range 4.7 to 37.3 ng Nm-2 s-1. These values are comparable to the range of fluxes from 2 to 83 ng Nm-2 s-1 reported from small scale field studies in a variety of tropical and sub-tropical locations reported in the review of Davidson and Kingerlee (1997). The fluxes calculated in the present study have been scaled up to cover the area of the Sahel bounded by 10 to 20 N and 10 E to 20W giving an estimated emission of up to 0.05 TgN from this area for July and August 2006. The observed chemical data also suggest that the NOx emitted from soils is taking part in ozone formation as ozone concentrations exhibit similar fine scale structure to the NOx, with enhancements over the wet soils. Such variability can not be explained on the basis of transport from other areas. [ABSTRACT FROM AUTHOR]

Nitrogen Oxide biogenic emissions from soils are driven by soil and environmental parameters. The relationship between these parameters and NO fluxes is highly non linear. A new algorithm, based on a neural network calculation, is used to reproduce the NO biogenic emissions in West Africa during the AMMA campaign, in August 2006. It has been coupled in the surface scheme of a coupled chemistry dynamics model to estimate the impact of the NO emissions on NOx and O3 formation in the lower troposphere. Four different simulations on the same domain and at the same period are compared: CTRL run (without soil NO emissions), YL95 run (with NO emissions inventory, at low time and space resolution), SOILNOx run (with NO emissions from neural network) and ALLNOx run (with NO from neural network). The influence of NOx from lightning is assessed, and is limited to the upper troposphere. Compared to parameterisations generally used at the global and regional scales, the neural network parameterisation can give higher NOx (up to +380 ppt) and ozone (up to +7ppb), closer to the ones measured in aircrafts during the AMMA field campaign. The NO emission from soils calculated with neural network responds to changes in soil moisture giving enhanced emissions over the wetted soil, as observed by aircraft measurements after the passing of a convective system, well reproduced by the model. Consecutive enhancement of NOx and ozone is limited to the lowest layers of the atmosphere in modelling, whereas measurements show higher levels above 500 m. This equation allows an immediate response of fluxes to environmental parameters, on the contrary to fixed emission inventories. The annual cycle of emissions from this algorithm will be simulated in a future work [ABSTRACT FROM AUTHOR]

Ultraviolet radiation is the key factor driving tropospheric photochemistry. It is strongly modulated by clouds and aerosols. A quantitative understanding of the radiation field and its effect on photochemistry is thus only possible with a detailed knowledge of the interaction between clouds and radiation. The overall objective of the project INSPECTRO was the characterization of the three-dimensional actinic radiation field under cloudy conditions. This was achieved during two measurement campaigns in Norfolk (East Anglia, UK) and Lower Bavaria (Germany) combining space-based, aircraft and ground-based measurements as well as simulations with the one-dimensional radiation transfer model UVSPEC and the three-dimensional radiation transfer model MYSTIC. During both campaigns the spectral actinic flux density was measured at several locations at ground level and in the air by up to four different aircraft. This allows the comparison of measured and simulated actinic radiation profiles. In addition satellite data were used to complete the information of the three dimensional input data set for the simulation. A three-dimensional simulation of actinic flux density data under cloudy sky conditions requires a realistic simulation of the cloud field to be used as an input for the 3-D radiation transfer model calculations. Two different approaches were applied, to derive high- and low-resolution data sets, with a grid resolution of about 100m and 1 km, respectively. The results of the measured and simulated radiation profiles as well as the results of the ground based measurements are presented in terms of photolysis rate profiles for ozone and nitrogen dioxide. During both campaigns all spectroradiometer systems agreed within ±10% if mandatory corrections e.g. stray light correction were applied. Stability changes of the systems were below 5% over the 4 week campaign periods and negligible over a few days. The J(O¹D) data of the single monochromator systems can be evaluated for zenith angles less than 70°, which was satisfied by nearly all airborne measurements during both campaigns. The comparison of the airborne measurements with corresponding simulations is presented for the total, downward and upward flux during selected clear sky periods of both campaigns. The compliance between the measured (from three aircraft) and simulated downward and total flux profiles lies in the range of ±15%. [ABSTRACT FROM AUTHOR]

Peroxy radicals (HO2+ΣRO2) were measured at the Weybourne Atmospheric Observatory (52° N, 1° E), Norfolk using a PEroxy Radical Chemical Amplifier (PERCA) during the winter and summer of 2002. The peroxy radical diurnal cycles showed a marked difference between the winter and summer campaigns with maximum concentrations of 12 pptv at midday in the summer and maximum concentrations as high as 30 pptv (10 min averages) in winter at night. The corresponding nighttime peroxy radical concentrations were not as high in summer (3 pptv). The peroxy radical concentration shows a distinct anti-correlation with increasing NOx during the daylight hours. At night, peroxy radicals increase with increasing NOx indicative of the role of NO3 chemistry. The average diurnal cycles for net ozone production, N(O3) show a large variability in ozone production, P(O3), and a large ozone loss, L(O3) in summer relative to winter. For a daylight average, net ozone production in summer than winter (1.51±0.5 ppbv h-1 and 1.11±0.47 ppbv h-1 respectively) but summer shows more variability of (meteorological) conditions than winter. The variability in NO concentration has a much larger effect on N(O3) than the peroxy radical concentrations. Photostationary state (PSS) calculations show an NO2 lifetime of 5min in summer and 21 min in the winter, implying that steady-state NO-NO2 ratios are not always attained during the winter months. The results show an active peroxy radical chemistry at night and the ability of winter to make oxidant. The net effect of this with respect to production of ozone in winter is unclear owing to the breakdown in the photostationary state. [ABSTRACT FROM AUTHOR]

Four halons (H-1301, H-1211, H-2402 and H-1202) have been measured in air samples collected from polar firn from Dome Concordia (Dome C), Antarctica, from Devon Island, Canada and the North Greenland Ice Core Project (NGRIP) site, Greenland. H-2402 and H-1202 are reported for the first time in firn air. The depth profiles show the concentrations of all four halons to be zero at the base of the firn thus demonstrating their entirely anthropogenic origin. This is the first evidence of this for H-2402 and H-1202. A 2-D atmospheric model was run to produce historical trends in the atmospheric concentrations at the firn sites, which were then input into a firn diffusion model to produce concentration depth profiles for comparison with the measurements. The firn measurements provide constraints on the atmospheric concentrations in both hemispheres which allow the global emission rates and their latitudinal distribution in the atmospheric model to be evaluated. Global emission trends previously determined from measurements at Cape Grim are found to be consistent with the firn data. Further emissions of H-1202 in recent years (late 1980s onwards) are likely to have come from latitudes mostly south of 40° N, but emissions prior to that may have come from further north. Emissions of H-1211 may also have shifted to latitudes south of 40° N during the late 1980s. The firn data is used to derive atmospheric trends in total organic bromine in the form of halons for both polar regions. [ABSTRACT FROM AUTHOR]