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Seasonal variation of aerosol size distributions in the free troposphere and residual layer at the puy de Dôme station, France

Particle number concentration and size distribution are important variables needed to constrain the role of atmospheric particles in the Earth radiation budget, both directly and indirectly through CCN activation. They are also linked to regulated variables such as particle mass (PM) and therefore of interest to air quality studies. However, data on their long-term variability are scarce, in particular at high altitudes. In this paper, we investigate the diurnal and seasonal variability of the aerosol total number concentration and size distribution at the puy de Dôme research station (France, 1465 m a.s.l.). We report a variability of aerosol particle total number concentration measured over a five-year (2003–2007) period for particles larger than 10 nm and aerosol size distributions between 10 and 500 nm over a two-year period (January 2006 to December 2007). Concentrations show a strong seasonality with maxima during summer and minima during winter. A diurnal variation is also observed with maxima between 12:00 and 18:00 UTC. At night (00:00–06:00 UTC), the median hourly total concentration varies from 600 to 800 cm−3 during winter and from 1700 to 2200 cm−3 during summer. During the day (08:00–18:00 UTC), the concentration is in the range of 700 to 1400 cm−3 during winter and of 2500 to 3500 cm−3 during summer. An averaged size distribution of particles (10–500 nm) was calculated for each season. The total aerosol number concentrations are dominated by the Aitken mode integral concentrations, which drive most of the winter to summer total concentrations increase. The night to day increase in dominated by the nucleation mode integral number concentration. Because the site is located in the free troposphere only a fraction of the time, in particular at night and during the winter season, we have subsequently analyzed the variability for nighttime and free tropospheric (FT)/residual layer (RL) conditions only. We show that a seasonal variability is still observed for these FT/RL conditions. The FT/RL seasonal variation is due to both seasonal changes in the air mass origin from winter to summer and enhanced concentrations of particles in the residual layer/free troposphere in summer. The later observation can be explained by higher emissions intensity in the boundary layer, stronger exchanges between the boundary layer and the free troposphere as well as enhanced photochemical processes. Finally, aerosols mean size distributions are calculated for a given air mass type (marine/continental/regional) according to the season for the specific conditions of the residual layer/free troposphere. The seasonal variability in aerosol sources seems to be predominant over the continent compared to the seasonal variation of marine aerosol sources. These results are of regional relevance and can be used to constrain chemical-transport models over Western Europe.
Airborne observations of total RONO2: new constraints on the yield and lifetime of isoprene nitrates

Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs), NO2, total peroxy nitrates (ΣPNs), HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5 h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.
Evolution of NOx emissions in Europe with focus on road transport control measures

European emission trends of nitrogen oxides since 1880 and up to present are presented here and are linked to the evolution of road transport emissions. Road transport has been the dominating source of NOx emissions since 1970, and contributes with 40% to the total emissions in 2005. Five trend regimes have been identified between 1880 and 2005. The first regime (1880–1950) is determined by a slow increase in fuel consumption all over Europe. The second regime (1950–1980) is characterized by a continued steep upward trend in liquid fuel use and by the introduction of the first regulations on road traffic emissions. Reduction in fuel consumption determines the emission trends in the third regime (1980–1990) that is also characterized by important differences between Eastern and Western Europe. Emissions from road traffic continue to grow in Western Europe in this period, and it is argued here that the reason for this continued NOx emission increase is related to early inefficient regulations for NOx in the transport sector. The fourth regime (1990–2000) involves a turning point for road traffic emissions, with a general decrease of emissions in Europe during that decade. It is in this period that we can identify the first emission reductions due to technological abatement in Western Europe. In the fifth regime (2000–2005), the economic recovery in Eastern Europe imposes increased emission from road traffic in this area. Western European emissions are on the other hand decoupled from the fuel consumption, and continue to decrease. The implementation of strict measures to control NOx emissions is demonstrated here to be a main reason for the continued Western European emission reductions. The results indicate that even though the effectiveness of European standards is hampered by a slow vehicle turnover, loopholes in the type-approval testing, and an increase in diesel consumption, the effect of such technical abatement measures is traceable in the evolution of European road traffic emissions over the last 15 years.
Closure on the single scattering albedo in the WRF-Chem framework using data from the MILAGRO campaign

Data from the MILAGRO field campaign, which took place in the Mexico City Metropolitan Area (MCMA) during March 2006, is used to perform a closure experiment between aerosol chemical properties and aerosol optical properties. Measured aerosol chemical properties, obtained from the MILAGRO T1 site, are fed to two different "chemical to optical properties" modules. One module uses a sectional approach and is identical to that used in the WRF-Chem model, while the other is based on a modal approach. This modal code is employed as an independent check on the WRF-Chem module. Both modules compute aerosol optical properties and, in particular, the single-scattering albedo, ϖ0, as a function of time. The single-scattering albedos are compared to independent measurements obtained from a photoacoustic spectrometer (PAS). Because chemical measurements of the aerosol coarse mode were not available, and the inlet of the PAS could not ingest aerosols larger than about 2 to 3 μm, we focus here on the fine-mode ϖ0. At 870 nm, the wavelength of the PAS measurements, the agreement between the computed (modal and WRF-Chem) and observed fine-mode ϖ0, averaged over the course of the campaign, is reasonably good. The observed ϖ0 value is 0.77, while for both modules, the calculated value was 0.75 resulting in a difference of 0.02 between observations and both computational approaches. This difference is less than the uncertainty of the observed ϖ0 values (6%, or 0.05), and therefore "closure" is achieved, at least for mean values. After adjusting some properties of black carbon absorption and mass concentration within plausible uncertainty limits, the two modules simulate well the diurnal variation of ϖ0, and the absorption coefficient, Babs, but are less successful in calculating the variation of the scattering coefficient, Bscat. This difficulty is probably caused by the presence of larger particles during the day when windblown dust is ubiquitous; this dust likely increases the proportion of large particles introduced into the PAS. The dust also contributes to a very large aerosol mass loading in the coarse mode, and neglect of the coarse mode may cause significant errors, estimated to be as large as 0.07, in the calculation and measurement of ambient ϖ0. Finally, the observed ϖ0 is compared to the ϖ0 computed by the full WRF-Chem model, which includes prognostic aerosol chemistry. Unlike the results discussed above, a comparison between observed and simulated ϖ0 values reveals major differences. This large discrepancy is probably due, in part, to poor characterization of emissions near the T1 site, particularly black carbon emissions.
The impact of biogenic carbon sources on aerosol absorption in Mexico City

In order to determine the wavelength dependence of fine (<1 micron) atmospheric aerosol absorption in the Mexico City area, the absorption Ångstrom exponents (AAEs) were calculated from hourly averages of aerosol absorption measured at seven wavelengths (370, 450, 520, 590, 660, 880, and 950 nm) with an aethalometer during two field campaigns, the Mexico City Metropolitan Area study in April 2003 (MCMA 2003) and the Megacity Initiative: Local and Global Research Observations in March 2006 (MILAGRO). These results were compared to AAEs determined in the laboratory from 850–280 nm (350 points) on 12-h fine aerosol samples collected at the same sites. The aerosol AAEs varied from 0.76 to 1.5 in 2003 and from 0.63 to 1.4 in 2006. The AAE values determined in the afternoon were consistently higher than the corresponding morning values, suggesting the photochemical aging of the aerosols leading to the formation of more highly UV absorbing organic aerosol species in the afternoon. The AAE values were compared to stable and radiocarbon isotopic measurements of the 12-h aerosol samples to determine the sources of the aerosol carbon. The fraction of modern carbon (fM) in the aerosol samples, as determined from<sup14C analysis, showed that an average of 70% of the carbonaceous aerosols in Mexico City were from modern biomass sources during both field campaigns. The 13C/12C ratios of the aerosol carbon illustrate the significant impact of Yucatan forest fires (C-3 plants) in 2003 and local grass fires (C-4 plants) in 2006. A direct comparison of the fM values, stable carbon isotope ratios, and aerosol AAEs suggested that the wavelength dependence of the aerosol absorption was controlled by the biogenically derived aerosol components.
Fossil and non-fossil sources of organic carbon (OC) and elemental carbon (EC) in Göteborg, Sweden

Particulate matter was collected at an urban site in Göteborg (Sweden) in February/March 2005 and in June/July 2006. Additional samples were collected at a rural site for the winter period. Total carbon (TC) concentrations were 2.1–3.6 μg m−3, 1.8–1.9 μg m−3, and 2.2–3.0 μg m−3 for urban/winter, rural/winter, and urban/summer conditions, respectively. Elemental carbon (EC), organic carbon (OC), water-insoluble OC (WINSOC), and water-soluble OC (WSOC) were analyzed for 14C in order to distinguish fossil from non-fossil emissions. As wood burning is the single major source of non-fossil EC, its contribution can be quantified directly. For non-fossil OC, the wood-burning fraction was determined independently by levoglucosan and 14C analysis and combined using Latin-hypercube sampling (LHS). For the winter period, the relative contribution of EC from wood burning to the total EC was >3 times higher at the rural site compared to the urban site, whereas the absolute concentrations of EC from wood burning were elevated only moderately at the rural compared to the urban site. Thus, the urban site is substantially more influenced by fossil EC emissions. For summer, biogenic emissions dominated OC concentrations most likely due to secondary organic aerosol (SOA) formation. During both seasons, a more pronounced fossil signal was observed for Göteborg than has previously been reported for Zurich, Switzerland. Analysis of air mass origin using back trajectories suggests that the fossil impact was larger when local sources dominated, whereas long-range transport caused an enhanced non-fossil signal. In comparison to other European locations, concentrations of levoglucosan and other monosaccharide anhydrides were low for the urban and the rural site in the area of Göteborg during winter.
Temperature dependence of yields of secondary organic aerosols from the ozonolysis of α-pinene and limonene

Secondary organic aerosol (SOA) formation has been investigated as a function of temperature and humidity for the ozone-initiated reaction of the two monoterpenes α-pinene (243–313 K) and limonene (253–313 K) using the 84.5 m3 aerosol chamber AIDA. This paper gives an overview of the measurements done and presents parameters specifically useful for aerosol yield calculations. The ozonolysis reaction, selected oxidation products and subsequent aerosol formation were followed using several analytical techniques for both gas and condensed phase characterisation. The effective densities of the SOA were determined by comparing mass and volume size distributions to (1.25±0.10) g cm−3 for α-pinene and (1.3±0.2) g cm−3 for limonene. The detailed aerosol dynamics code COSIMA-SOA proved to be essential for a comprehensive evaluation of the experimental results and for providing parameterisations directly applicable within atmospheric models. The COSIMA-assisted analysis succeeded to reproduce the observed time evolutions of SOA total mass, number and size distributions by adjusting the following properties of two oxidation product proxies: individual yield parameters (αi), partitioning coefficients (Ki), vapour pressures (pi) and effective accommodation coefficients (γi). For these properties temperature dependences were derived and parameterised. Vapour pressures and partitioning coefficients followed classical Clausius – Clapeyron temperature dependences. From this relationship enthalpies of vaporisation were derived for the two more and less volatile product proxies of α-pinene: (59±8) kJ mol−1 and (24±9) kJ mol−1, and limonene: (55±14) kJ mol−1 and (25±12) kJ mol−1. The more volatile proxy components had a notably low enthalpy of vaporisation while the less volatile proxy components gave enthalpies of vaporisation comparable with those of typical products from α-pinene oxidation, e.g. pinonaldehyde and pinonic acid.
The Tropical Tropopause Layer 1960–2100

The representation of the Tropical Tropopause Layer (TTL) in 13 different Chemistry Climate Models (CCMs) designed to represent the stratosphere is analyzed. Simulations for 1960–2005 and 1980–2100 are analyzed. Simulations for 1960–2005 are compared to reanalysis model output. CCMs are able to reproduce the basic structure of the TTL. There is a large (10 K) spread in annual mean tropical cold point tropopause temperatures. CCMs are able to reproduce historical trends in tropopause pressure obtained from reanalysis products. Simulated historical trends in cold point tropopause temperatures are not consistent across models or reanalyses. The pressure of both the tropical tropopause and the level of main convective outflow appear to have decreased (increased altitude) in historical runs as well as in reanalyses. Decreasing pressure trends in the tropical tropopause and level of main convective outflow are also seen in the future. Models consistently predict decreasing tropopause and convective outflow pressure, by several hPa/decade. Tropical cold point temperatures are projected to increase by 0.09 K/decade. Tropopause anomalies are highly correlated with tropical surface temperature anomalies and with tropopause level ozone anomalies, less so with stratospheric temperature anomalies. Simulated stratospheric water vapor at 90 hPa increases by up to 0.5–1 ppmv by 2100. The result is consistent with the simulated increase in temperature, highlighting the correlation of tropopause temperatures with stratospheric water vapor.
Laboratory studies of ice formation pathways from ammonium sulfate particles

Cirrus clouds are composed of ice particles and their formation pathways have been studied extensively in the laboratory. The ability of ammonium sulfate particles to act as nuclei for cirrus clouds has been of particular importance because of their ubiquitous presence in the upper troposphere. The results of past laboratory experiments of homogeneous ice nucleation from ammonium sulfate particles show a wide range of freezing conditions. In the present study, a flow tube apparatus equipped with Fourier transform infrared spectroscopy was used to reexamine these discrepancies. It was found that when ammonium sulfate particles were preconditioned at 100% relative humidity (RH) prior to experimentation, the particles began to freeze at conditions predicted by the homogeneous ice nucleation model developed by Koop et al. (2000). If the particles were not preconditioned at 100% RH, some froze at warmer temperatures and lower ice saturation ratios than predicted by Koop et al. (2000). It is hypothesized that a population of effloresced particles affected freezing conditions for particles that were not preconditioned at 100% RH.
SCIAMACHY formaldehyde observations: constraint for isoprene emission estimates over Europe?

Formaldehyde (HCHO) is an important intermediate compound in the degradation of volatile organic compounds (VOCs) in the troposphere. Sources of HCHO are largely dominated by its secondary production from VOC oxidation, methane and isoprene being the main precursors in unpolluted areas. As a result of the moderate lifetime of HCHO, its spatial distribution is determined by reactive hydrocarbon emissions. We focus here on Europe and investigate the influence of the different emissions on HCHO tropospheric columns with the CHIMERE chemical transport model in order to interpret the comparisons between SCIAMACHY and simulated HCHO columns. Europe was never specifically studied before for these purposes using satellite observations. The bias between measurements and model is less than 20% on average. The differences are discussed according to the errors on the model and the observations and remaining discrepancies are attributed to a misrepresentation of biogenic emissions. This study requires the characterisation of: (1) the model errors and performances concerning formaldehyde. The errors on the HCHO columns, mainly related to chemistry and mixed emission types, are evaluated to 2×1015 molecule/cm2 and the model performances evaluated using surface measurements are satisfactory (~13%); (2) the observation errors that define the needs in spatial and temporal averaging for meaningful comparisons. Using SCIAMACHY observations as constraint for biogenic isoprene emissions in an inverse modelling scheme reduces their uncertainties by about a factor of two in region of intense emissions. The retrieved correction factors for the isoprene emissions range from a factor of 0.15 (North Africa) to a factor of 2 (Poland, the United Kingdom) depending on the regions.