Distance-dependent energy transfer occurs from the Metal-to-Ligand Charge Transfer (MLCT) excited state to an anthracene-acrylate derivative (Acr-An) incorporated into the polymer network of a semirigid poly(ethyleneglycol)dimethacrylate monolith. Following excitation, to Acr-An triplet energy transfer occurs followed by long-range, Acr- 3 An—Acr-An → Acr-An—Acr- 3 An, energy migration. With methyl viologen dication (MV 2+ ) added as a trap, Acr- 3 An + MV 2+ → Acr-An + + MV + electron transfer results in sensitized electron transfer quenching over a distance of approximately 90 Å.
Abstract. Ozone and its precursors were measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the monsoon season 2006 as part of the African Monsoon Multidisciplinary Analysis (AMMA) campaign. One of the main features observed in the west African boundary layer is the increase of the ozone mixing ratios from 25 ppbv over the forested area (south of 12° N) up to 40 ppbv over the Sahelian area. We employ a two-dimensional (latitudinal versus vertical) meteorological model coupled with an O3-NOx-VOC chemistry scheme to simulate the distribution of trace gases over West Africa during the monsoon season and to analyse the processes involved in the establishment of such a gradient. Including an additional source of NO over the Sahelian region to account for NO emitted by soils we simulate a mean NOx concentration of 0.7 ppbv at 16° N versus 0.3 ppbv over the vegetated region further south in reasonable agreement with the observations. As a consequence, ozone is photochemically produced with a rate of 0.25 ppbv h−1 over the vegetated region whilst it reaches up to 0.75 ppbv h−1 at 16° N. We find that the modelled gradient is due to a combination of enhanced deposition to vegetation, which decreases the ozone levels by up to 11 pbbv, and the aforementioned enhanced photochemical production north of 12° N. The peroxy radicals required for this enhanced production in the north come from the oxidation of background CO and CH4 as well as from VOCs. Sensitivity studies reveal that both the background CH4 and partially oxidised VOCs, produced from the oxidation of isoprene emitted from the vegetation in the south, contribute around 5–6 ppbv to the ozone gradient. These results suggest that the northward transport of trace gases by the monsoon flux, especially during nighttime, can have a significant, though secondary, role in determining the ozone gradient in the boundary layer. Convection, anthropogenic emissions and NO produced from lightning do not contribute to the establishment of the discussed ozone gradient.
Abstract. 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 height allow the flux of pollutants to be calculated. Extrapolation gives annual emissions for CO, NOx and VOCs of 0.72 Tg C yr−1, 0.02 Tg N yr−1 and 0.28 Tg C yr−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.
Intercontinental Transport of Ozone and Precursors (ITOP) (part of International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)) was an intense research effort to measure long‐range transport of pollution across the North Atlantic and its impact on O 3 production. During the aircraft campaign plumes were encountered containing large concentrations of CO plus other tracers and aerosols from forest fires in Alaska and Canada. A chemical transport model, p‐TOMCAT, and new biomass burning emissions inventories are used to study the emissions long‐range transport and their impact on the troposphere O 3 budget. The fire plume structure is modeled well over long distances until it encounters convection over Europe. The CO values within the simulated plumes closely match aircraft measurements near North America and over the Atlantic and have good agreement with MOPITT CO data. O 3 and NO x values were initially too great in the model plumes. However, by including additional vertical mixing of O 3 above the fires, and using a lower NO 2 /CO emission ratio (0.008) for boreal fires, O 3 concentrations are reduced closer to aircraft measurements, with NO 2 closer to SCIAMACHY data. Too little PAN is produced within the simulated plumes, and our VOC scheme's simplicity may be another reason for O 3 and NO x model‐data discrepancies. In the p‐TOMCAT simulations the fire emissions lead to increased tropospheric O 3 over North America, the north Atlantic and western Europe from photochemical production and transport. The increased O 3 over the Northern Hemisphere in the simulations reaches a peak in July 2004 in the range 2.0 to 6.2 Tg over a baseline of about 150 Tg.
Abstract. We report here top-down emissions estimates 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 height allow the flux of pollutants to be calculated. Extrapolation gives annual emissions for CO, NOx, and VOCs of 1.44 Tg yr−1, 0.03 Tg yr−1 and 0.37 Tg yr−1 respectively with uncertainties of +250/−60%. These inferred emissions are consistent with bottom-up estimates for other developing megacities and are attributed to the evaporation of fuels, mobile combustion and natural gas emissions.
More than half the world's rainforest has been lost to agriculture since the Industrial Revolution. Among the most widespread tropical crops is oil palm (Elaeis guineensis): global production now exceeds 35 million tonnes per year. In Malaysia, for example, 13% of land area is now oil palm plantation, compared with 1% in 1974. There are enormous pressures to increase palm oil production for food, domestic products, and, especially, biofuels. Greater use of palm oil for biofuel production is predicated on the assumption that palm oil is an "environmentally friendly" fuel feedstock. Here we show, using measurements and models, that oil palm plantations in Malaysia directly emit more oxides of nitrogen and volatile organic compounds than rainforest. These compounds lead to the production of ground-level ozone (O(3)), an air pollutant that damages human health, plants, and materials, reduces crop productivity, and has effects on the Earth's climate. Our measurements show that, at present, O(3) concentrations do not differ significantly over rainforest and adjacent oil palm plantation landscapes. However, our model calculations predict that if concentrations of oxides of nitrogen in Borneo are allowed to reach those currently seen over rural North America and Europe, ground-level O(3) concentrations will reach 100 parts per billion (10(9)) volume (ppbv) and exceed levels known to be harmful to human health. Our study provides an early warning of the urgent need to develop policies that manage nitrogen emissions if the detrimental effects of palm oil production on air quality and climate are to be avoided.
Abstract. 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 1×107 molecules cm–3) are calculated to be in the range 4.7 to 37.3 ng N m−2 s−1. These values are comparable to the range of fluxes from 2 to 83 ng N m−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 20 W 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.
This paper is based on alkyl nitrate measurements made over the North Atlantic as part of the International Consortium for Research on Atmospheric Transport and Transformation (ICARTT). The focus is on the analysis of air samples collected on the UK BAe‐146 aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) project, but air samples collected on board the NASA DC‐8 and NOAA WP‐3D aircraft as part of a Lagrangian experiment are also used. The ratios between the alkyl nitrates and their parent hydrocarbons are compared with those expected from chemical theory. Further, a box model is run to investigate the temporal evolution of the alkyl nitrates in three Lagrangian case studies and compared to observations. The air samples collected during ITOP do not appear to be strongly influenced by oceanic sources, but rather are influenced by emissions from the N.E. United States and from Alaskan fires. There also appears to be a widespread common source of ethyl nitrate and 1‐propyl nitrate other than from their parent hydrocarbons. The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place. The observations in the more photochemically processed air masses are consistent with the alkyl nitrate production reactions no longer dominating the peroxy radical self/cross reactions. Further, the results also suggest that the rates of photochemical processing in the Alaskan smoke plumes were small.
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