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[1] The composition of the planetary boundary layer in regions of deep tropical convection has a profound impact on the Tropical Tropopause Layer (TTL). The Aerosol and Chemical Transport in tropIcal conVEction (ACTIVE) aircraft campaign was conducted from November 2005 to February 2006 from Darwin, Australia, to characterize the influence of both monsoonal and localized land-based deep convection on the composition of the TTL. This paper summarizes the composition of the potential inflow to such convection in terms of aerosol particle size and composition, carbon monoxide, and ozone, as measured in the lowest 4 km of the atmosphere by the NERC Dornier-228 aircraft during 28 flights in different meteorological regimes over the course of ACTIVE. Six contrasting periods are identified in the boundary layer background as a result of the prevailing meteorology and sources of pollution. The campaign began with a relatively polluted and variable biomass burning season in November, followed by a transition to the monsoon season through December with much less burning. A clean maritime flow dominated the wet-active, and dry-inactive, monsoon period in January; it was followed by a monsoon break period in February, with a return to continental flow and a more premonsoon background state. Deep convective systems, capable of transporting boundary layer air to the TTL, were observed daily outside of the monsoon periods. The chemical composition of submicron aerosols in the premonsoon periods was dominated by a mix of fresh and aged organic material with significant black carbon, well-correlated with carbon monoxide indicating a common burning source, while marine aerosol during the monsoon changed markedly between the wet and dry phases. High concentrations of coarse-mode aerosols were also observed in the monsoon: the clean, marine air masses and high surface winds imply that sea salt may be the dominant aerosol type under these conditions. The climatology presented here will provide a valuable data set for model simulation of chemical and aerosol transport by deep convection in the Darwin region.Citation: Allen, G., et al. (2008), Aerosol and trace-gas measurements in the Darwin area during the wet season,

Abstract. The biogenic volatile organic compound (BVOC) composition of ambient air at a rural field site near Djougou, Benin has been studied as part of the AMMA (African Monsoon Multidisciplinary Analysis) project. Ambient air was sampled during day and night during the period 2 June 2006 to 13 June 2006. Gas samples from within the forest canopy and from branch and cuvette enclosure systems for four vegetation species were also obtained and emissions flux estimates made. All samples were analysed for the presence of isoprene, monoterpenes and sesquiterpenes by either gas chromatography-time of flight mass spectrometry (GC-TOF/MS) or comprehensive gas chromatography-time of flight mass spectrometry (GCxGC-TOF/MS). Concentrations of isoprene ranged from a few tens of pptV to in excess of 3000 pptV. Similar concentration ranges for certain monoterpenes were also observed. Limonene was seen at a maximum concentration in ambient air of 5000 pptV. The combination of leaf-level observations and direct analysis of dried vegetation samples suggests that emissions of terpene species from indigenous species are unlikely to account for the unexpectedly high ambient concentrations of monoterpenes. Leaf scale emission measurements and biological sample analysis indicated that Anacardium occidentale, a non-native crop species found throughout the tropics, was the dominant source of monoterpenes at this location. These preliminary findings suggest that activities involving species replacement have potential implications for the chemistry of the African troposphere that have not been widely considered previously.

This paper reports observations of a tropospheric chemical equator in the Western Pacific region during the Austral monsoon season, separating the polluted Northern Hemisphere from the cleaner Southern Hemisphere. Measurements of carbon monoxide, ozone, aerosol size/composition, and non‐methane hydrocarbons were made from aircraft, flying north from Darwin, Australia as part of the Aerosol and Chemical Transport In tropical conVEction (ACTIVE) campaign. A chemical equator, defined as a sharp gradient in the chemical background, was found not to be coincident with the Intertropical Convergence Zone during this period. A pronounced interfacial region was identified between 8.5 and 10°S, where tracer mixing ratios increased rapidly within the boundary layer, e.g. CO from 40 ppbv to 160 ppbv within 0.5° latitude (50 km), with inhibited inter‐hemispheric mixing. These measurements are discussed in context using a combination of meteorological and Earth‐observing satellite imagery, back trajectory analysis and chemical model data with the conclusion that air flowing into and subsequently uplifted by the active convection of the Tropical Warm Pool (TWP) region in the Western Pacific is likely to be highly polluted, and will perturb the composition of the Tropical Tropopause Layer. The main source of CO and other pollutants within the TWP region is expected to be biomass burning, with extensive fires in North Sumatra and Thailand during this period. The sharp gradient in composition at the chemical equator seen here results from extensive burning to the north, contrasting with pristine maritime air advected from the Southern Indian Ocean by a strong land‐based cyclone over the Northern Territory of Australia.

Space-borne column measurements of formaldehyde (HCHO), a high-yield oxidation product of volatile organic compounds (VOCs), represent important constraints for quantifying net regional fluxes of VOCs. Here, we interpret observed distributions of HCHO columns from the Global Ozone Monitoring Experiment (GOME) over tropical South America during 1997-2001. We present the first comparison of year-long in situ isoprene concentrations and fire-free GOME HCHO columns over a tropical ecosystem. GOME HCHO columns and in situ isoprene concentrations are elevated in the wet and dry seasons, with the highest values in the dry season. Previous analysis of the in situ data highlighted the possible role of drought in determining the elevated concentrations during the dry season, inferring the potential of HCHO columns to provide regional-scale constraints for estimating the role of drought on isoprene emissions. The agreement between the observed annual cycles of GOME HCHO columns and Along-Track Scanning Radiometer firecount data over the Amazon basin (correlations typically greater than 0.75 for a particular year) illustrates the potential of HCHO column to provide quantitative information about biomass burning emissions.

Abstract. The biogenic volatile organic compound (BVOC) composition of ambient air at a rural field site near Djougou, Benin has been studied as part of the AMMA (African Monsoon Multidisciplinary Analysis) project. Ambient air was sampled during day and night during the period 2 June 2006 to 13 June 2006. Gas samples from within the forest canopy and from branch and cuvette enclosure systems for four vegetation species were also obtained and emissions flux estimates made. All samples were analysed for the presence of isoprene, monoterpenes and sesquiterpenes by either gas chromatography-time of flight mass spectrometry (GC-TOF/MS) or comprehensive gas chromatography-time of flight mass spectrometry (GCxGC-TOF/MS). Concentrations of isoprene ranged from a few tens of pptV to in excess of 3000 pptV. Similar concentration ranges for certain monoterpenes were also observed. Limonene was seen at a maximum concentration in ambient air of 5000 pptV. The combination of leaf-level observations and direct analysis of dried vegetation samples suggest that emissions of terpene species from indigenous species are unlikely to account for the unexpectedly high ambient concentrations of monoterpenes. Leaf scale emission measurements and biological sample analysis indicated that Anacardium occidentale, a non-native crop species found throughout the tropics, was the dominant source of monoterpenes at this location. These preliminary findings suggest that activities involving species replacement have potential implications for the chemistry of the African troposphere that have not been widely considered previously.

The free energy of transfer of the proton between water and water-rich mixtures of water and 2-ethoxyethanol has been determined experimentally by investigating spectrophotometrically the competition of 4-nitroaniline for two solvated protonated species, one containing water molecules alone and the other containing, in addition, a molecule of 2-ethoxyethanol. Using these values of AGF(H+), AG:(Cl-) has been calculated from AG?(HCI). pK values for organic acids in water-2-ethoxyethanol have been combined with the AGy(H+) values to produce free energies of transfer of the charge alone on these organic molecules for both positive and negative ions. All these free energies of transfer are compared with values obtained in mixtures of other co-solvents with water. To aid this, the relative partial molar volumes of water and of 2-ethoxyethanol in their mixtures have been calculated from the variation of density with solvent composition.

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