Controls of carbon dioxide concentrations and fluxes above central London

Eddy-covariance measurements of carbon dioxide fluxes were taken semi-continuously between October 2006 and May 2008 at 190 m height in central London (UK) to quantify emissions and study their controls. Inner London, with a population of 8.2 million (~5000 inhabitants per km2) is heavily built up with 8% vegetation cover within the central boroughs. CO2 emissions were found to be mainly controlled by fossil fuel combustion (e.g. traffic, commercial and domestic heating). The measurement period allowed investigation of both diurnal patterns and seasonal trends. Diurnal averages of CO2 fluxes were found to be highly correlated to traffic. However changes in heating-related natural gas consumption and, to a lesser extent, photosynthetic activity that controlled the seasonal variability. Despite measurements being taken at ca. 22 times the mean building height, coupling with street level was adequate, especially during daytime. Night-time saw a higher occurrence of stable or neutral stratification, especially in autumn and winter, which resulted in data loss in post-processing. No significant difference was found between the annual estimate of net exchange of CO2 for the expected measurement footprint and the values derived from the National Atmospheric Emissions Inventory (NAEI), with daytime fluxes differing by only 3%. This agreement with NAEI data also supported the use of the simple flux footprint model which was applied to the London site; this also suggests that individual roughness elements did not significantly affect the measurements due to the large ratio of measurement height to mean building height.

Relationships between human population density and burned area at continental and global scales

We explore the large spatial variation in the relationship between population density and burned area, using continental-scale Geographically Weighted Regression (GWR) based on 13 years of satellite-derived burned area maps from the global fire emissions database (GFED) and the human population density from the gridded population of the world (GPW 2005). Significant relationships are observed over 51.5% of the global land area, and the area affected varies from continent to continent: population density has a significant impact on fire over most of Asia and Africa but is important in explaining fire over < 22% of Europe and Australia. Increasing population density is associated with both increased and decreased in fire. The nature of the relationship depends on land-use: increasing population density is associated with increased burned are in rangelands but with decreased burned area in croplands. Overall, the relationship between population density and burned area is non-monotonic: burned area initially increases with population density and then decreases when population density exceeds a threshold. These thresholds vary regionally. Our study contributes to improved understanding of how human activities relate to burned area, and should contribute to a better estimate of atmospheric emissions from biomass burning.

The impact of traffic emissions on atmospheric ozone and OH: results from QUANTIFY

To estimate the impact of emissions by road, aircraft and ship traffic on ozone and OH in the present-day atmosphere six different atmospheric chemistry models have been used. Based on newly developed global emission inventories for road, ship and aircraft emission data sets each model performed sensitivity simulations reducing the emissions of each transport sector by 5%. The model results indicate that on global annual average lower tropospheric ozone responds most sensitive to ship emissions (50.6%±10.9% of the total traffic induced perturbation), followed by road (36.7%±9.3%) and aircraft exhausts (12.7%±2.9%), respectively. In the northern upper troposphere between 200–300 hPa at 30–60° N the maximum impact from road and ship are 93% and 73% of the maximum effect of aircraft, respectively. The latter is 0.185 ppbv for ozone (for the 5% case) or 3.69 ppbv when scaling to 100%. On the global average the impact of road even dominates in the UTLS-region. The sensitivity of ozone formation per NOx molecule emitted is highest for aircraft exhausts. The local maximum effect of the summed traffic emissions on the ozone column predicted by the models is 0.2 DU and occurs over the northern subtropical Atlantic extending to central Europe. Below 800 hPa both ozone and OH respond most sensitively to ship emissions in the marine lower troposphere over the Atlantic. Based on the 5% perturbation the effect on ozone can exceed 0.6% close to the marine surface (global zonal mean) which is 80% of the total traffic induced ozone perturbation. In the southern hemisphere ship emissions contribute relatively strongly to the total ozone perturbation by 60%–80% throughout the year. Methane lifetime changes against OH are affected strongest by ship emissions up to 0.21 (± 0.05)%, followed by road (0.08 (±0.01)%) and air traffic (0.05 (± 0.02)%). Based on the full scale ozone and methane perturbations positive radiative forcings were calculated for road emissions (7.3±6.2 mWm−2) and for aviation (2.9±2.3 mWm−2). Ship induced methane lifetime changes dominate over the ozone forcing and therefore lead to a net negative forcing (−25.5±13.2 mWm−2).

Latitudinal variation of the effect of aviation NOx emissions on atmospheric ozone and methane and related climate metrics

We evaluate the response to regional and latitudinal changes in aircraft NOx emissions using several climate metrics (radiative forcing (RF), Global Warming Potential (GWP), Global Temperature change Potential (GTP)). Global chemistry transport model integrations were performed with sustained perturbations in regional aircraft and aircraft-like NOx emissions. The RF due to the resulting ozone and methane changes is then calculated. We investigate the impact of emission changes for specific geographical regions (approximating to USA, Europe, India and China) and cruise altitude emission changes in discrete latitude bands covering both hemispheres. We find that lower latitude emission changes (per Tg N) cause ozone and methane RFs that are about a factor of 6 larger than those from higher latitude emission changes. The net RF is positive for all experiments. The meridional extent of the RF is larger for low latitude emissions. GWPs for all emission changes are positive, with tropical emissions having the largest values; the sign of the GTP depends on the choice of time horizon.

Sensitivity of biogenic isoprene emissions to past, present and future environmental conditions and implications for atmospheric chemistry.

[1] We have implemented a process-based isoprene emission model in the HadGEM2 Earth-system model with coupled atmospheric chemistry in order to examine the feedback between isoprene emission and climate. Isoprene emissions and their impact on atmospheric chemistry and climate are estimated for preindustrial (1860–1869), present-day (2000–2009), and future (2100–2109) climate conditions. The estimate of 460 TgC/yr for present-day global total isoprene emission is consistent with previous estimates. Preindustrial isoprene emissions are estimated to be 26% higher than present-day. Future isoprene emissions using the RCP8.5 scenario are similar to present-day because increased emissions resulting from climate warming are countered by CO2 inhibition of isoprene emissions. The impact of biogenic isoprene emissions on the global O3 burden and CH4 lifetime is small but locally significant, and the impact of changes in isoprene emissions on atmospheric chemistry depends strongly on the state of climate and chemistry.

Establishing Lagrangian connections between observations within air masses crossing the Atlantic during the International Consortium for Atmospheric Research on Transport and Transformation experiment

The ITCT-Lagrangian-2K4 (Intercontinental Transport and Chemical Transformation) experiment was conceived with an aim to quantify the effects of photochemistry and mixing on the transformation of air masses in the free troposphere away from emissions. To this end, attempts were made to intercept and sample air masses several times during their journey across the North Atlantic using four aircraft based in New Hampshire (USA), Faial (Azores) and Creil (France). This article begins by describing forecasts from two Lagrangian models that were used to direct the aircraft into target air masses. A novel technique then identifies Lagrangian matches between flight segments. Two independent searches are conducted: for Lagrangian model matches and for pairs of whole air samples with matching hydrocarbon fingerprints. The information is filtered further by searching for matching hydrocarbon samples that are linked by matching trajectories. The quality of these "coincident matches'' is assessed using temperature, humidity and tracer observations. The technique pulls out five clear Lagrangian cases covering a variety of situations and these are examined in detail. The matching trajectories and hydrocarbon fingerprints are shown, and the downwind minus upwind differences in tracers are discussed.

Biogenic nitric oxide emissions from soils: impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Analysis) - observational study

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. NO 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 (1×106 to 1×107 molecules cm−3) are calculated to be in the range 8.4 to 36.1 ng N m−2 s−1. These values are comparable to the range of fluxes from 0.5 to 28 ng N m−2 s−1 reported from small scale field studies in a variety of non-nutrient rich 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 0.03 to 0.30 Tg N 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. Delon et al. (2008) is a companion paper to this one which models the impact of soil NOx emissions on the NOx and ozone concentration over West Africa during AMMA. It employs an artificial neural network to define the emissions of NOx from soils, integrated into a coupled chemistry-dynamics model. The results are compared to the observed data presented in this paper. Here we compare fluxes deduced from the observed data with the model-derived values from Delon et al. (2008).

Biogenic nitric oxide emissions from soils: impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Analysis) - Modelling study

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 linked to precipitations in the Sahel on the 6 August 2006 during the AMMA campaign. This algorithm has been coupled in the surface scheme of a coupled chemistry dynamics model (MesoNH Chemistry) to estimate the impact of the NO emissions on NOx and O3 formation in the lower troposphere for this particular episode. Four different simulations on the same domain and at the same period are compared: one with anthropogenic emissions only, one with soil NO emissions from a static inventory, at low time and space resolution, one with NO emissions from neural network, and one with NO from neural network plus lightning NOx. The influence of NOx from lightning is limited to the upper troposphere. 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. The subsequent enhancement of NOx and ozone is limited to the lowest layers of the atmosphere in modelling, whereas measurements show higher concentrations above 1000 m. The neural network algorithm, applied in the Sahel region for one particular day of the wet season, allows an immediate response of fluxes to environmental parameters, unlike static emission inventories. Stewart et al (2008) is a companion paper to this one which looks at NOx and ozone concentrations in the boundary layer as measured on a research aircraft, examines how they vary with respect to the soil moisture, as indicated by surface temperature anomalies, and deduces NOx fluxes. In this current paper the model-derived results are compared to the observations and calculated fluxes presented by Stewart et al (2008).

Direct estimates of emissions from the megacity of Lagos

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.

Direct estimates of emissions from the megacity of Lagos

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.

U.K. HiGEM: Simulations of desert dust and biomass burning aerosols with a high-resolution atmospheric GCM

The atmospheric component of the United Kingdom’s new High-resolution Global Environmental Model (HiGEM) has been run with interactive aerosol schemes that include biomass burning and mineral dust. Dust emission, transport, and deposition are parameterized within the model using six particle size divisions, which are treated independently. The biomass is modeled in three nonindependent modes, and emissions are prescribed from an external dataset. The model is shown to produce realistic horizontal and vertical distributions of these aerosols for each season when compared with available satellite- and ground-based observations and with other models. Combined aerosol optical depths off the coast of North Africa exceed 0.5 both in boreal winter, when biomass is the main contributor, and also in summer, when the dust dominates. The model is capable of resolving smaller-scale features, such as dust storms emanating from the Bode´ le´ and Saharan regions of North Africa and the wintertime Bode´ le´ low-level jet. This is illustrated by February and July case studies, in which the diurnal cycles of model variables in relation to dust emission and transport are examined. The top-of-atmosphere annual mean radiative forcing of the dust is calculated and found to be globally quite small but locally very large, exceeding 20 W m22 over the Sahara, where inclusion of dust aerosol is shown to improve the model radiative balance. This work extends previous aerosol studies by combining complexity with increased global resolution and represents a step toward the next generation of models to investigate aerosol–climate interactions. 1. Introduction Accurate modeling of mineral dust is known to be important because of its radiative impact in both numerical weather prediction models (Milton et al. 2008; Haywood et

Reactions of NO3 with the man-made emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene, ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone

Rate coefficients for reactions of nitrate radicals (NO3) with the anthropogenic emissions 2-methylpent-2-ene, (Z)-3-methylpent-2-ene.. ethyl vinyl ether, and the stress-induced plant emission ethyl vinyl ketone (pent-1-en-3-one) were determined to be (9.3 +/- 1.1) x 10(-12), (9.3 +/- 3.2) x 10(-12), (1.7 +/- 1.3) x 10(-12) and (9.4 + 2.7) x 10(-17) cm(3) molecule(-1) s(-1). We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. Experiments with ethyl vinyl ether required a modification of our established procedure that might introduce additional uncertainties, and the errors suggested reflect these difficulties. Rate coefficients are discussed in terms of electronic and steric influences. Atmospheric lifetimes with respect to important oxidants in the troposphere were calculated. NO3-initiated oxidation is found to be the strongly dominating degradation route for 2-methylpent-2-ene, (Z)-3-methylpent-2-ene and ethyl vinyl ether. Atmospheric concentrations of the alkenes and their relative contribution to the total NMHC emissions from trucks can be expected to increase if plans for the introduction of particle filters for diesel engines are implemented on a global scale. Thus more kinetic data are required to better evaluate the impact of these emissions.

Long-lived halocarbon trends and budgets from atmospheric chemistry modelling constrained with measurements in polar firn

The budgets of seven halogenated gases (CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, CCl4 and SF6) are studied by comparing measurements in polar firn air from two Arctic and three Antarctic sites, and simulation results of two numerical models: a 2-D atmospheric chemistry model and a 1-D firn diffusion model. The first one is used to calculate atmospheric concentrations from emission trends based on industrial inventories; the calculated concentration trends are used by the second one to produce depth concentration profiles in the firn. The 2-D atmospheric model is validated in the boundary layer by comparison with atmospheric station measurements, and vertically for CFC-12 by comparison with balloon and FTIR measurements. Firn air measurements provide constraints on historical atmospheric concentrations over the last century. Age distributions in the firn are discussed using a Green function approach. Finally, our results are used as input to a radiative model in order to evaluate the radiative forcing of our target gases. Multi-species and multi-site firn air studies allow to better constrain atmospheric trends. The low concentrations of all studied gases at the bottom of the firn, and their consistency with our model results confirm that their natural sources are small. Our results indicate that the emissions, sinks and trends of CFC-11, CFC-12, CFC-113, CFC-115 and SF6 are well constrained, whereas it is not the case for CFC-114 and CCl4. Significant emission-dependent changes in the lifetimes of halocarbons destroyed in the stratosphere were obtained. Those result from the time needed for their transport from the surface where they are emitted to the stratosphere where they are destroyed. Efforts should be made to update and reduce the large uncertainties on CFC lifetimes.

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO3 in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO3. The rate coefficients were determined to be (1.53 +/- 0.23) x 10(-13) and (1.39 +/- 0.19) x 10(-14) cm(3) molecule(-1) s(-1) for reactions of NO3 with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N2O5 as source of NO3 resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO2 allowed us to determine the rate coefficients for the N2O5 reactions to be (5.0 +/- 2.8) x 10(-19) cm(3) molecule(-1) s(-1) for (Z)-pent-2-en-1-ol, and (9.1 +/- 5.8) x 10(-19) cm(3) molecule(-1) s(-1) for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.

A study of the ethene-ozone reaction with photoelectron spectroscopy: measurement of product branching ratios and atmospheric implications

The ozone-ethene reaction has been investigated at low pressure in a flow-tube interfaced to a u.v. photoelectron spectrometer. Photoelectron spectra recorded as a function of reaction time have been used to estimate partial pressures of the reagents and products, using photoionization cross-sections for selected photoelectron bands of the reagents and products, which have been measured separately. Product yields compare favourably with results of other studies, and the production of oxygen and acetaldehyde have been measured as a function of time for the first time. A reaction scheme developed for the ozone-ethene reaction has been used to simulate the reagents and products as a function of time. The results obtained are in good agreement with the experimental measurements. For each of the observed products, the simulations allow the main reaction (or reactions) for production of that product to be established. The product yields have been used in a global model to estimate their global annual emissions in the atmosphere. Of particular interest are the calculated global annual emissions of formaldehyde (0.96 ± 0.10 Tg) and formic acid, (0.05 ± 0.01 Tg) which are estimated as 0.04% and 0.7% of the total annual emission respectively.