ALBERT

Description: Broadband cavity enhanced absorption spectroscopy (BBCEAS) has been used to measure the sum of concentrations of NO3 and N2O5 from the BT (telecommunications) Tower 160 m above street level in central London during the REPARTEE II campaign in October and November 2007. Substantial variability was observed in these night-time nitrogen compounds: peak NO3+N2O5 mixing ratios reached 800 pptv, whereas the mean night-time NO3+N2O5 was approximately 30 pptv. Additionally, [NO3+N2O5] showed negative correlations with [NO] and [NO2] and a positive correlation with [O3]. Co-measurements of temperature and NO2 from the BT Tower were used to calculate the equilibrium partitioning between NO3 and N2O5 which was always found to strongly favour N2O5 (NO3/N2O5=0.01 to 0.04). Two methods are used to calculate the lifetimes for NO3 and N2O5, the results being compared and discussed in terms of the implications for the night-time oxidation of nitrogen oxides and the night-time sinks for NOy.

Description: Broadband cavity enhanced absorption spectroscopy (BBCEAS) has been used to measure the sum of concentrations of NO3 and N2O5 from the BT (telecommunications) Tower 160 m above street level in central London during the REPARTEE II campaign in October and November 2007. Substantial variability was observed in these night-time nitrogen compounds: peak NO3+N2O5 mixing ratios reached 800 pptv, whereas the mean night-time NO3+N2O5 was approximately 30 pptv. Additionally, [NO3+N2O5] showed negative correlations with [NO] and [NO2] and a positive correlation with [O3]. Co-measurements of temperature and NO2 from the BT Tower were used to calculate the equilibrium partitioning between NO3 and N2O5 which was always found to strongly favour N2O5 (NO3/N2O5=0.01 to 0.04). Two methods are used to calculate the lifetimes for NO3 and N2O5, the results being compared and discussed in terms of the implications for the night-time oxidation of nitrogen oxides and the night-time sinks for NOy.

Description: Much uncertainty in the value of the imaginary part of the refractive index of mineral dust contributes to uncertainty in the radiative effect of mineral dust in the atmosphere. A synthesis of optical, chemical and physical in-situ aircraft measurements from the DODO experiments during February and August 2006 are used to calculate the refractive index mineral dust encountered over West Africa. Radiative transfer modeling and measurements of broadband shortwave irradiance at a range of altitudes are used to test and validate these calculations for a specific dust event on 23 August 2006 over Mauritania. Two techniques are used to determine the refractive index: firstly a method combining measurements of scattering, absorption, size distributions and Mie code simulations, and secondly a method using composition measured on filter samples to apportion the content of internally mixed quartz, calcite and iron oxide-clay aggregates, where the iron oxide is represented by either hematite or goethite and clay by either illite or kaolinite. The imaginary part of the refractive index at 550 nm (ni550) is found to range between 0.0001 i to 0.0046 i, and where filter samples are available, agreement between methods is found depending on mineral combination assumed. The refractive indices are also found to agree well with AERONET data where comparisons are possible. ni550 is found to vary with dust source, which is investigated with the NAME model for each case. The relationship between both size distribution and ni550 on the accumulation mode single scattering albedo at 550 nm (ω0550) are examined and size distribution is found to have no correlation to ω0550, while ni550 shows a strong linear relationship with ω0550. Radiative transfer modeling was performed with different models (Mie-derived refractive indices, but also filter sampling composition assuming both internal and external mixing). Our calculations indicate that Mie-derived values of ni550 and the externally mixed dust where the iron oxide-clay aggregate corresponds to the goethite-kaolinite combination result in the best agreement with irradiance measurements. The radiative effect of the dust is found to be very sensitive to the mineral combination (and hence refractive index) assumed, and to whether the dust is assumed to be internally or externally mixed.

Description: During a 4-week run in October–November 2006, a pilot experiment was performed at the CERN Proton Synchrotron in preparation for the Cosmics Leaving OUtdoor Droplets (CLOUD) experiment, whose aim is to study the possible influence of cosmic rays on clouds. The purpose of the pilot experiment was firstly to carry out exploratory measurements of the effect of ionising particle radiation on aerosol formation from trace H2SO4 vapour and secondly to provide technical input for the CLOUD design. A total of 44 nucleation bursts were produced and recorded, with formation rates of particles above the 3 nm detection threshold of between 0.1 and 100 cm−3s−1, and growth rates between 2 and 37 nm h−1. The corresponding H2O concentrations were typically around 106 cm−3 or less. The experimentally-measured formation rates and H2SO4 concentrations are comparable to those found in the atmosphere, supporting the idea that sulphuric acid is involved in the nucleation of atmospheric aerosols. However, sulphuric acid alone is not able to explain the observed rapid growth rates, which suggests the presence of additional trace vapours in the aerosol chamber, whose identity is unknown. By analysing the charged fraction, a few of the aerosol bursts appear to have a contribution from ion-induced nucleation and ion-ion recombination to form neutral clusters. Some indications were also found for the accelerator beam timing and intensity to influence the aerosol particle formation rate at the highest experimental SO2 concentrations of 6 ppb, although none was found at lower concentrations. Overall, the exploratory measurements provide suggestive evidence for ion-induced nucleation or ion-ion recombination as sources of aerosol particles. However in order to quantify the conditions under which ion processes become significant, improvements are needed in controlling the experimental variables and in the reproducibility of the experiments. Finally, concerning technical aspects, the most important lessons for the CLOUD design include the stringent requirement of internal cleanliness of the aerosol chamber, as well as maintenance of extremely stable temperatures (variations below 0.1 °C

Description: We synthesised observations of total particle number (CN) concentration from 36 sites around the world. We found that annual mean CN concentrations are typically 300–2000 cm−3 in the marine boundary layer and free troposphere (FT) and 1000–10 000 cm−3 in the continental boundary layer (BL). Many sites exhibit pronounced seasonality with summer time concentrations a factor of 2–10 greater than wintertime concentrations. We used these CN observations to evaluate primary and secondary sources of particle number in a global aerosol microphysics model. We found that emissions of primary particles can reasonably reproduce the spatial pattern of observed CN concentration (R2=0.46) but fail to explain the observed seasonal cycle (R2=0.1). The modeled CN concentration in the FT was biased low (normalised mean bias, NMB=−88%) unless a secondary source of particles was included, for example from binary homogeneous nucleation of sulfuric acid and water (NMB=−25%). Simulated CN concentrations in the continental BL were also biased low (NMB=−74%) unless the number emission of anthropogenic primary particles was increased or a mechanism that results in particle formation in the BL was included. We ran a number of simulations where we included an empirical BL nucleation mechanism either using the activation-type mechanism (nucleation rate, J, proportional to gas-phase sulfuric acid concentration to the power one) or kinetic-type mechanism (J proportional to sulfuric acid to the power two) with a range of nucleation coefficients. We found that the seasonal CN cycle observed at continental BL sites was better simulated by BL particle formation (R2=0.3) than by increasing the number emission from primary anthropogenic sources (R2=0.18). The nucleation constants that resulted in best overall match between model and observed CN concentrations were consistent with values derived in previous studies from detailed case studies at individual sites. In our model, kinetic and activation-type nucleation parameterizations gave similar agreement with observed monthly mean CN concentrations.

Description: In this study we investigate ultrafine particle (UFP) fluxes using a first order eddy viscosity turbulence closure Computational Fluid Dynamics (CFD) model and determine the different factors that influence emissions of UFP into the urban boundary layer. Both vertical turbulent fluxes as well as the fluxes due to mean circulatory flow are shown to contribute to the overall ventilation characteristics of street canyons. We then derive a simple parameterised numerical prediction model for canyon top UFP venting which is then compared with tower based micrometeorological flux measurements obtained during the REPARTEE & CityFlux field experiments.

Description: Data from seven cruises in three different environments including the Pearl River estuary, sewage discharge outfall and eastern coastal/shelf waters, were used to examine the seasonal variations in net primary production (NPP) and the biologically active gases O2 and CO2. In the winter dry season, when monsoon-induced downwelling was dominant, NPP was low (−60±50 mmol C m−2 d−1) in all three regions. The negative NPP corresponded to low O2 influxes (−100±50 mmol O2 m−2 d−1) and CO2 effluxes (24±10 mmol C m−2 d−1). In the summer wet season, when upwelling brought the bottom oceanic waters to the nearshore due to the southwest monsoonal wind, there was a 2 to 15-fold increase in integrated primary production (IPP) compared to winter. The increase in IPP was likely due to the favorable conditions such as stratification and the nutrient inputs from upwelled waters and the Pearl River estuary. NPP reached up to 240±100 mmol C m−2 d−1 in the wet season. However, accompanying the high positive NPP, we observed an influx of O2 (−100±60 mmol O2 m−2 d−1) and efflux of CO2 (25±15 mmol C m−2 d−1). The high positive NPP corresponding to a CO2 source and O2 sink could be explained by the influence of the southwest monsoon-induced upwelling, as the upwelling brought cold, low DO (160±30 μM) and high DIC (1960±100 μatm) water to the surface in the wet season. Hence, the subtropical Hong Kong coastal waters are generally a CO2 source due to the monsoonal influence in both the dry and wet seasons.

Description: A process-based fire regime model (SPITFIRE) has been developed, coupled with ecosystem dynamics in the LPJ Dynamic Global Vegetation Model, and used to explore spatial and temporal patterns of fire regimes and the current impact of fire on the terrestrial carbon cycle and associated emissions of trace atmospheric constituents. The model estimates an average release of 2.24 Pg C yr−1 as CO2 from biomass burning during the 1980s and 1990s. Comparison with observed active fire counts shows that the model reproduces where fire occurs and can mimic broad geographic patterns in the peak fire season, although the predicted peak is 1–2 months late in some regions. Modelled fire season length is generally overestimated by about one month, but shows a realistic pattern of differences among biomes. Comparisons with remotely sensed burnt-area products indicate that the model reproduces broad geographic patterns of annual fractional burnt area over most regions, including the boreal forest, although interannual variability in the boreal zone is underestimated. Overall SPITFIRE produces realistic simulations of spatial and temporal patterns of fire under modern conditions and of the current impact of fire on the terrestrial carbon cycle and associated emissions of trace greenhouse gases and aerosols.

Description: Urban boundary layers (UBLs) can be highly complex due to the heterogeneous roughness and heating of the surface, particularly at night. Due to a general lack of observations, it is not clear whether canonical models of boundary layer mixing are appropriate in modelling air quality in urban areas. This paper reports Doppler lidar observations of turbulence profiles in the centre of London, UK, as part of the second REPARTEE campaign in autumn 2007. Lidar-measured standard deviation of vertical velocity averaged over 30 min intervals generally compared well with in situ sonic anemometer measurements at 190 m on the BT telecommunications tower. During calm, nocturnal periods, the lidar underestimated turbulent mixing due mainly to limited sampling rate. Mixing height derived from the turbulence, and aerosol layer height from the backscatter profiles, showed similar diurnal cycles ranging from ca. 300 to 800 m, increasing to ca. 200 to 850 m under clear skies. The aerosol layer height was sometimes significantly different to the mixing height, particularly at night under clear skies. For convective and neutral cases, the scaled turbulence profiles resembled canonical results; this was less clear for the stable case. Lidar observations clearly showed enhanced mixing beneath stratocumulus clouds reaching down on occasion to approximately half daytime boundary layer depth. On one occasion the nocturnal turbulent structure was consistent with a nocturnal jet, suggesting a stable layer. Given the general agreement between observations and canonical turbulence profiles, mixing timescales were calculated for passive scalars released at street level to reach the BT Tower using existing models of turbulent mixing. It was estimated to take ca. 10 min to diffuse up to 190 m, rising to between 20 and 50 min at night, depending on stability. Determination of mixing timescales is important when comparing to physico-chemical processes acting on pollutant species measured simultaneously at both the ground and at the BT Tower during the campaign. From the 3 week autumnal data-set there is evidence for occasional stable layers in central London, effectively decoupling surface emissions from air aloft.

Description: We have incorporated a semi-mechanistic isoprene emission module into the JULES land-surface scheme. We evaluate the coupled model against local above-canopy isoprene emission flux measurements from six flux tower sites as well as satellite-derived estimates of isoprene emission over tropical South America and east and south Asia. The model simulates diurnal variability well: correlation coefficients are significant (at the 95% level) for all flux tower sites. The model reproduces day-to-day variability with significant correlations (at the 95% confidence level) at four of the six flux tower sites. At the UMBS site, a complete set of seasonal observations is available for two years (2000 and 2002). The model reproduces the seasonal pattern of emission during 2002, but does less well in the year 2000. Comparison with the satellite-derived isoprene-emission estimates suggests that the model simulates the main spatial patterns, seasonal and inter-annual variability over tropical regions. The model yields a global annual isoprene emission during the 1990s of 380 ± 7 TgC yr−1.