Aerosol simulations in chemistry transport models (CTMs) still suffer from numerous uncertainties, and diagnostic evaluations are required to point out major error sources. This paper presents an ...original approach to evaluate CTMs based on local and imported contributions in a large megacity rather than urban background concentrations. The study is applied to the CHIMERE model in the Paris region (France) and considers the fine particulate matter (PM2.5) and its main chemical constituents (elemental and organic carbon, nitrate, sulfate and ammonium), for which daily measurements are available during a whole year at various stations (PARTICULES project). Back-trajectory data are used to locate the upwind station, from which the concentration is identified as the import, the local production being deduced from the urban concentration by subtraction. Uncertainties on these contributions are quantified. Small biases in urban background PM2.5 simulations (bias of +16%) hide significant error compensations between local and advected contributions, as well as in PM2.5 chemical compounds. In particular, winter time organic matter (OM) imports appear strongly underestimated while local OM and elemental carbon (EC) production is overestimated all along the year. Erroneous continental wood burning emissions and missing secondary organic aerosol (SOA) pathways may explain errors on advected OM, while the carbonaceous compounds is likely to be related to errors in emissions and dynamics. A statistically significant local formation of nitrate is also highlighted from observations, but missed by the model. Together with the overestimation of nitrate imports, it leads to a bias of +51% on the local PM2.5 contribution. Such an evaluation finally gives more detailed insights on major gaps in current CTMs on which future efforts are needed.
The ozone–NOy photochemistry is explored in contrasting polluted plumes sampled with the Safire ATR 42 research aircraft during three summer field international campaigns in the megacity Paris, the ...North West Mediterranean basin (WMB) and southern West Africa (SWA). Various metrics derived from the photostationary steady state (PSS) and the ozone production efficiency (OPE) are calculated from airborne observations. A new metric, the oxidant production rate normalized to carbon monoxide (PROx), is introduced and quantified as a function of the processing time of the plume. In most of the polluted plumes, it is found that the Leighton ratio (F) characterizing the equilibrium between O3 and NOx is, on average, within the PSS range (1 0.32) or greater. The positive dependence of Ox to NO usually indicates a VOC-sensitive regime inside the plumes with some exceptions. In Paris, under oceanic westerly winds, and during DACCIWA, the plumes show a rural-like chemistry behaviour at moderate NOx levels (NOx-sensitive). Intense and frequent rapid changes in J(NO2), NO and NO2 explain the deviations from the PSS. The OPE for Paris plume suggests that the VOC-sensitive regime extends far beyond the urban plume. The mean ozone production is higher downwind of Paris (30 ppb h1 on average) compared to SWA (20 ppb h-1) and WMB (6 ppb h1). PROx values vary between 0 (no oxidantproduction) and 0.27 ppbOx ppbCO1 h1. The determined uncertainty on the Leighton ratio value could affect the differences in the estimation of the photochemical oxidant production by PO3 and PROx. The emissions of CO along the flight path and the presence of vegetation and high humidity levels might shape the oxidant production depending on the explored environment. While limited in number, PROx values set a benchmark for future photochemical studies to compare with: Paris as representative of an anthropogenic urban plume and WMB as representative of a biogenic continental plume.
An ensemble Kalman filter (EnKF) has been coupled to the CHIMERE chemical transport model in order to assimilate ozone ground-based measurements on a regional scale. The number of ensembles is ...reduced to 20, which allows for future operational use of the system for air quality analysis and forecast. Observation sites of the European ozone monitoring network have been classified using criteria on ozone temporal variability, based on previous work by Flemming et al. (2005). This leads to the choice of specific subsets of suburban, rural and remote sites for data assimilation and for evaluation of the reference run and the assimilation system. For a 10-day experiment during an ozone pollution event over Western Europe, data assimilation allows for a significant improvement in ozone fields: the RMSE is reduced by about a third with respect to the reference run, and the hourly correlation coefficient is increased from 0.75 to 0.87. Several sensitivity tests focus on an a posteriori diagnostic estimation of errors associated with the background estimate and with the spatial representativeness of observations. A strong diurnal cycle of both these errors with an amplitude up to a factor of 2 is made evident. Therefore, the hourly ozone background error and the observation error variances are corrected online in separate assimilation experiments. These adjusted background and observational error variances provide a better uncertainty estimate, as verified by using statistics based on the reduced centered random variable. Over the studied 10-day period the overall EnKF performance over evaluation stations is found relatively unaffected by different formulations of observation and simulation errors, probably due to the large density of observation sites. From these sensitivity tests, an optimal configuration was chosen for an assimilation experiment extended over a three-month summer period. It shows a similarly good performance as the 10-day experiment.
The accurate determination of nitrogen dioxide (NO2) tropospheric vertical columns from satellite measurements depends strongly on the airmass factor (AMF) used. A sensitivity study was performed ...with the radiative transfer model SCIATRAN to better understand the impact of aerosols on the calculation of NO2 AMFs. This influence was studied by varying the NO2 and aerosol vertical distributions, as well as physical and optical properties of the particles. In terms of aerosol definitions, the key factors for these calculations were identified as the relation between trace gas and aerosol vertical profiles, the optical depth of the aerosol layer, and single scattering albedo. In addition, surface albedo also has a large impact on the calculations. Overall it was found that particles mixed with the trace gas increases the measurements' sensitivity, but only when the aerosol is not very absorbing. The largest change, a factor of ~2 relative to the situation without aerosols, was found when a low layer of aerosol (600 m) was combined with a homogenous NO2 layer of 1.0 km. A layer of aerosol above the NO2 usually reduces the sensitivity of the satellite measurement. This situation is found mostly for runs with discrete elevated aerosol layers (representative for long-range transport) that can generate a decrease of the AMF values of up to 70%. The use of measured aerosol profiles and modelled NO2 resulted, generally, in much smaller changes of AMF relative to the pure Rayleigh case. Exceptions are some events of elevated layers with high aerosol optical depth that lead to a strong decrease of the AMF values. These results highlight the importance of aerosols in the retrieval of tropospheric NO2 columns from space and indicate the need for detailed information on aerosol properties and vertical distribution.
This paper investigates the impact of biogenic isoprene and terpene emissions on photochemical species levels in the French Ile‐de‐France region during several photooxidant pollution episodes in ...summer 1998 and 1999 during the Atmospheric Pollution Over the Paris Area (ESQUIF) project. The effect of biogenic emissions on both ozone produced on a continental scale and advected in Ile‐de‐France and on ozone locally formed are assessed. For this purpose, simulations with and without biogenic emissions are performed with a nested version of the CHIMERE model. This chemistry transport model includes both a continental (western European) domain with 0.5° horizontal resolution and a regional domain (Ile‐de‐France) of 150 × 150 km extension with a horizontal resolution of 6 km. An emissions database for biogenic isoprene and terpene emissions from forests has been set up. These emissions are estimated using emission factors for different tree species recently revised by Simpson et al. 1999 and for different land use data sets, including highly resolved (1 km) satellite measurements for Ile‐de‐France. Good agreement has been found between modeled and measured (by aircraft) isoprene levels (overall bias <10%), which lends confidence to the use of the emissions database for subsequent simulations. The comparison between runs with and without biogenic volatile organic compound (VOC) emissions indicates a significant difference in ozone in Ile‐de‐France, up to 40 ppb for one extreme day. Biogenic VOC emissions from Ile‐de‐France along with those from outside the Ile‐de‐France region have an approximately equal responsibility for the additional ozone buildup. The main reason for this increased ozone formation is the enhancement of radicals due to larger concentrations of carbonyl species and ozone and their subsequent photolysis. Biogenic emissions lead to a shift in the sensitivity to emissions (toward more “NOx‐limited”). However, generally, either with or without biogenic emissions, a “VOC‐limited” regime is simulated over the Ile‐de‐France region.
The content and evolution of brown carbon (BrC) in smokes from Siberian forest fires were analyzed using measurements of the aerosol absorption optical depth (AAOD) at three Russian AERONET stations ...located in Tomsk, Zvenigorod, and Yekaterinburg. Estimates are obtained of the relative contribution of BrC in fine aerosol particles to the absorption of solar radiation at a wavelength of 440 nm (η
BrC
) and, in particular, for an anomalous episode of long-range transport of smokes from Siberia to the European part of Russia in summer 2016. A considerable BrC content is found in smokes in Tomsk and Zvenigorod (where η
BrC
is estimated to be 15 and 18% on average). It is noteworthy that no significant η
BrC
values were revealed during passage of smokes from Siberian fires over Yekaterinburg. The η
BrC
values were found to decrease with aerosol aging under sunlit conditions on the characteristic timescale of about 30 h. At the same time, the measurements in Zvenigorod indicate that the absorption properties of the organic component of smoke aerosol increase during a much longer evolution.
In this paper, we examine the extent to which an ensemble generated from a single air quality model correctly represents the global uncertainty of ozone simulations with a regional scale ...chemistry-transport model and whether it is suitable for ozone data assimilation. An ensemble of 30 members is constructed from a reference simulation in which the model parameters that are the most uncertain for determining ozone concentrations are randomly perturbed. Comparisons of the simulated ensemble using the model CHIMERE with observations are examined over the summer season both at the surface and higher in the troposphere. Although the ensemble overestimates vertical and horizontal correlation between errors, the average model error is well represented both at the surface and in the vertical dimension (after an adjustment for the latter). A variability of about 7–8
ppb is found. The results found in this study with respect to tropospheric ozone model errors and error correlation lengths both from ensemble simulations and model to observation comparisons are of particular interest for data assimilation when constructing model error covariance matrices.
We present here the development and first field deployment of a novel Aircraft-based Laser ABlation Aerosol MAss spectrometer (ALABAMA), which is capable of measuring the chemical composition and ...size of individual ambient aerosol particles in the size range between 150 and 900 nm. The instrument uses a continuous wave 532 nm laser to size and detect the particles, a pulsed 266 nm laser to ablate and ionize the particles, and a bipolar, Z-shaped time-of-flight mass spectrometer to detect positive and negative ions. The ALABAMA fits into a 19"-aircraft rack of 150 cm height and has a total weight of 140 kg, thus currently being one of the smallest and lightest-weight instruments of its type. We present a detailed characterization of ALABAMA with respect to particle beam width, detection and ablation efficiency, and example mass spectra of different particle types. The first aircraft-based field mission was performed within the MEGAPOLI summer campaign in July 2009 around Paris, France, onboard an ATR42 aircraft. During 11 research flights, corresponding to a total measuring time of approximately 44 hours, ALABAMA measured 6502 single particle mass spectra. The mass spectra were classified into eight particle classes using distinctive markers for each particle type. The most abundant particle types contained organic and secondary inorganic compounds. The results further show that differences in the abundance of observed particle types between different air masses are very pronounced when comparing air masses arriving from the greater Paris area with air masses arriving from other directions.
For the investigation of megacity emission development and the impact outside the source region, mobile aerosol and trace gas measurements were carried out in the Paris metropolitan area between 1 ...July and 31 July 2009 (summer conditions) and 15 January and 15 February 2010 (winter conditions) in the framework of the European Union FP7 MEGAPOLI project. Two mobile laboratories, MoLa and MOSQUITA, were deployed, and here an overview of these measurements and an investigation of the applicability of such measurements for the analysis of megacity emissions are presented. Both laboratories measured physical and chemical properties of fine and ultrafine aerosol particles as well as gas phase constituents of relevance for urban pollution scenarios. The applied measurement strategies include cross-section measurements for the investigation of plume structure and quasi-Lagrangian measurements axially along the flow of the city's pollution plume to study plume aging processes. Results of intercomparison measurements between the two mobile laboratories represent the adopted data quality assurance procedures. Most of the compared measurement devices show sufficient agreement for combined data analysis. For the removal of data contaminated by local pollution emissions a video tape analysis method was applied. Analysis tools like positive matrix factorization and peak integration by key analysis applied to high-resolution time-of-flight aerosol mass spectrometer data are used for in-depth data analysis of the organic particulate matter. Several examples, including a combination of MoLa and MOSQUITA measurements on a cross section through the Paris emission plume, are provided to demonstrate how such mobile measurements can be used to investigate the emissions of a megacity. A critical discussion of advantages and limitations of mobile measurements for the investigation of megacity emissions completes this work.
The HOVERT (HOrizontal and VERtical Transport of ozone and particulate matter) campaign held in the Berlin Brandenburg area in Eastern Germany from September 2001 to September 2002 allowed to collect ...a unique data set of the aerosol chemical speciation (daily averages) at traffic, urban and rural sites. These observations are used for a thorough evaluation of the aerosol part in the REM-CALGRID model (RCG) developed at the Free University of Berlin (FUB). For inorganic ions (sulphate, nitrate and ammonium), simulated annual averages agree to observations within ±30% at more than half of the sites and always within a factor of two. Correlation coefficients are larger than in previous studies for SO42− and NH4+ (>0.7). For nitrate, less elevated correlations, 0.4–0.7 in the cold season, 0.2–0.4 in the warm season, are encountered. To our knowledge, this is one of the first comparisons of air quality model simulated elemental and organic carbon (EC and OC) with daily observations for a whole year. It suggests an overestimation of EC and OC emissions in the Berlin area (through a scaling techniques between EC, OC and NOx and when assuming correct NOx emissions), and an underestimation of EC and OC at rural sites. Secondary organic aerosol (SOA) formation, recently introduced into the model (SORGAM module, Schell et al., 2001), is simulated as a very variable process, SOA levels varying from close to zero for most days to more than 5 μg/m3. Correlation between simulated SOA to observed OC is about 0.6, indicating that simulated variability partly corresponds to reality.
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