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The relationship between 0.25–2.5 μm aerosol and CO2 emissions over a city

Unlike exhaust emissions, non-exhaust traffic emissions are completely unregulated and in addition, there are large uncertainties in the non-exhaust emission factors required to estimate the emissions of these aerosols. This study provides the first published results of direct measurements of size resolved emission factors for particles in the size range 0.25–2.5 μm using a new approach to derive aerosol emission factors based on carbon dioxide (CO2) emission fluxes. Aerosol fluxes were measured over one year using the eddy covariance method at the top of a 105 m high communication tower in Stockholm, Sweden. Maximum CO2 and particle fluxes were found when the wind direction coincided with the area of densest traffic within the footprint area. Negative fluxes (uptake of CO2 and deposition of particles) coincided with periods of sampling from an urban forest area. The fluxes of CO2 were used to obtain emission factors for particles by assuming that the CO2 fluxes could be directly related to the amount of fuel burnt by vehicles in the footprint area. The estimated emission factor for the fleet mix in the measurement area was, in number 1.8 × 1011 particle veh−1 km−1 (for 0.25–2.5 μm size range). Assuming spherical particles of density 1600 kg m−3 this corresponds to 27.5 mg veh−1 km−1. For particles (0.8–2.5 μm) the emission factors were 5.1 × 109 veh−1 km−1 for number and 11.5 mg veh−1 km−1 for mass. But a wind speed dependence was noted for high wind speeds. Thus, for wind speeds larger than 9 m s−1, as measured in the tower at 105 m (U105), the emission factor for particle number and mass was parameterised as: Ef (Number, 0.8–2.5 μm) = (6.1 ± 1.7)109 U105 −50 ± 188 and Ef (Mass, 0.8–2.5 μm) = (20 ± 12) U105 − 171 ±122.
Measurement from sun-synchronous orbit of a reaction rate controlling the diurnal NOx cycle in the stratosphere

A reaction rate associated with the nighttime formation of an important diurnally varying species, N2O5, is determined from MIPAS-ENVISAT. During the day, photolysis of N2O5 in the stratosphere contributes to nitrogen-catalysed ozone destruction. However, at night concentrations of N2O5 increase, temporarily sequestering reactive NOx NO and NO2 in a natural cycle which regulates the majority of stratospheric ozone. In this paper, the reaction rate controlling the formation of N2O5 is determined from this instrument for the first time. The observed reaction rate is compared to the currently accepted rate determined from laboratory measurements. Good agreement is obtained between the observed and accepted experimental reaction rates within the error bars.
Emissions of isoprenoids and oxygenated biogenic volatile organic compounds from a New England mixed forest

Fluxes of biogenic volatile organic compounds, including isoprene, monoterpenes, and oxygenated VOCs measured above a mixed forest canopy in central Massachusetts during the 2005 and 2007 growing seasons are reported. Mixing ratios were measured using proton transfer reaction mass spectrometry (PTR-MS) and fluxes computed by the disjunct eddy covariance technique. Isoprene was by far the predominant BVOC emitted at this site, with summer mid-day average fluxes of 5.3 and 4.4 mg m−2 hr−1 in 2005 and 2007, respectively. In comparison, mid-day average fluxes of monoterpenes were 0.21 and 0.15 mg m−2 hr−1 in each of these years. On short times scales (days), the diel pattern in emission rate compared well with a standard emission algorithm for isoprene. The general shape of the seasonal cycle and the observed decrease in isoprene emission rate in early September was, however, not well captured by the model. Monoterpene emission rates exhibited dependence on light as well as temperature, as determined from the improved fit to the observations obtained by including a light-dependent term in the model. The mid-day average flux of methanol from the canopy was 0.14 mg m−2 hr−1 in 2005 and 0.19 mg m−2 hr−1 in 2007, but the maximum flux was observed in spring (29 May 2007), when the flux reached 1.0 mg m−2 hr−1. This observation is consistent with enhanced methanol production during leaf expansion. Summer mid-day fluxes of acetone were 0.15 mg m−2 hr−1 during a short period in 2005, but only 0.03 mg m−2 h−1 averaged over 2007. Episodes of negative fluxes of oxygenated VOCs, particularly acetone, were observed periodically, especially in 2007. Thus, deposition within the canopy could help explain the low season-averaged flux of acetone in 2007. Fluxes of species of biogenic origin at mass-to-charge ($m/z$) ratios of 73 (0.05 mg m−2 hr−1 in 2005; 0.03 mg m−2 hr−1 in 2007) and 153 (5 μg m−2 hr−1 in 2007), possibly corresponding to methyl ethyl ketone and an oxygenated terpene or methyl salicylate, respectively, were also observed.
First space-based derivation of the global atmospheric methanol emission fluxes

This study provides improved methanol emission estimates on the global scale, in particular for the largest methanol source, the terrestrial biosphere, and for biomass burning. To this purpose, one complete year of spaceborne measurements of tropospheric methanol columns retrieved for the first time by the thermal infrared sensor IASI aboard the MetOp satellite are compared with distributions calculated by the IMAGESv2 global chemistry-transport model. Two model simulations are performed using a priori biogenic methanol emissions either from the new MEGANv2.1 emission model, which is fully described in this work and is based on net ecosystem flux measurements, or from a previous parameterization based on net primary production by Jacob et al. (2005). A significantly better model performance in terms of both amplitude and seasonality is achieved through the use of MEGANv2.1 in most world regions, with respect to IASI data, and to surface- and air-based methanol measurements, even though important discrepancies over several regions are still present. As a second step of this study, we combine the MEGANv2.1 and the IASI column abundances over continents in an inverse modelling scheme based on the adjoint of the IMAGESv2 model to generate an improved global methanol emission source. The global optimized source totals 187 Tg yr−1 with a contribution of 100 Tg yr−1 from plants, only slightly lower than the a priori MEGANv2.1 value of 105 Tg yr−1. Large decreases with respect to the MEGANv2.1 biogenic source are inferred over Amazonia (up to 55 %) and Indonesia (up to 58 %), whereas more moderate reductions are recorded in the Eastern US (20–25 %) and Central Africa (25–35 %). On the other hand, the biogenic source is found to strongly increase in the arid and semi-arid regions of Central Asia (up to a factor of 5) and Western US (factor of 2), probably due to a source of methanol specific to these ecosystems which is unaccounted for in the MEGANv2.1 inventory. The most significant error reductions achieved by the optimization concern the derived biogenic emissions over the Amazon and over the Former Soviet Union. The robustness of the derived fluxes to changes in convective updraft fluxes, in methanol removal processes, and in the choice of the biogenic a priori inventory is assessed through sensitivity inversions. Detailed comparisons of the model with a number of aircraft and surface observations of methanol, as well as new methanol measurements in Europe and in the Reunion Island show that the satellite-derived methanol emissions improve significantly the agreement with the independent data, giving thus credence to the IASI dataset.
Modeling chemistry in and above snow at Summit, Greenland – Part 1: Model description and results

Sun-lit snow is increasingly recognized as a chemical reactor that plays an active role in uptake, transformation, and release of atmospheric trace gases. Snow is known to influence boundary layer air on a local scale, and given the large global surface coverage of snow may also be significant on regional and global scales. We present a new detailed one-dimensional snow chemistry module that has been coupled to the 1-D atmospheric boundary layer model MISTRA. The new 1-D snow module, which is dynamically coupled to the overlaying atmospheric model, includes heat transport in the snowpack, molecular diffusion, and wind pumping of gases in the interstitial air. The model includes gas phase chemical reactions both in the interstitial air and the atmosphere. Heterogeneous and multiphase chemistry on atmospheric aerosol is considered explicitly. The chemical interaction of interstitial air with snow grains is simulated assuming chemistry in a liquid-like layer (LLL) on the grain surface. The coupled model, referred to as MISTRA-SNOW, was used to investigate snow as the source of nitrogen oxides (NOx) and gas phase reactive bromine in the atmospheric boundary layer in the remote snow covered Arctic (over the Greenland ice sheet) as well as to investigate the link between halogen cycling and ozone depletion that has been observed in interstitial air. The model is validated using data taken 10 June–13 June, 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). The model predicts that reactions involving bromide and nitrate impurities in the surface snow can sustain atmospheric NO and BrO mixing ratios measured at Summit, Greenland during this period.
Deposition of dinitrogen pentoxide, N2O5, to the snowpack at high latitudes

Dinitrogen pentoxide, N2O5, is an important nighttime intermediate in the oxidation of NOx that is hydrolysed on surfaces. We conducted a field campaign in Fairbanks, Alaska during November 2009 to measure the gradient and derive a flux (and deposition velocity) of N2O5 depositing to snowpack using the aerodynamic gradient method. The deposition velocity of N2O5 under Arctic winter conditions was found to be 0.59 ± 0.47 cm s−1, which is the first measurement of this parameter to our knowledge. Based on the measured deposition velocity, we compared the chemical loss rate of N2O5 via snowpack deposition to the total steady state loss rate and found that deposition to snowpack is at least 1/8th of the total chemical removal of N2O5 that is located within the first few meters above the ground surface.
The influence of the stratosphere on the tropospheric zonal wind response to CO2 doubling

The influence of a CO2 doubling on the stratospheric potential vorticity (PV) is examined in two climate models. Subsequently, the influence of changes in the stratosphere on the tropospheric zonal wind response is investigated, by inverting the stratospheric PV. Radiative effects seem to dominate the stratospheric response to CO2 doubling in the Southern Hemisphere. These lead to a stratospheric PV increase at the edge of the polar vortex, resulting in an increased westerly influence of the stratosphere on the troposphere, increasing the midlatitude tropospheric westerlies in late winter. In the Northern Hemisphere, dynamical effects are also important. Both models show a reduced polar PV and an enhanced midlatitude PV in the Northern Hemisphere winter stratosphere. These PV changes are likely related to an enhanced wave forcing of the winter stratosphere, as measured by an increase in the 100 hPa eddy heat flux, and result in a reduced westerly influence of the stratosphere on the high latitude tropospheric winds. In one model, the high latitude PV decreases are, however, restricted to higher altitudes, and the tropospheric response due to the stratospheric changes is dominated by an increased westerly influence in the midlatitudes, related to the increase in midlatitude PV in the lower stratosphere. The tropospheric response in zonal wind due to the stratospheric PV changes is of the order of 0.5 to 1 m s−1. The total tropospheric response has a somewhat different spatial structure, but is of similar magnitude. This indicates that the stratospheric influence is of importance in modifying the tropospheric zonal wind response to CO2 doubling.
Atmospheric new particle formation: real and apparent growth of neutral and charged particles

In this study we have provided simple analytical formulae to estimate the growth rate of a nucleation mode due to self-coagulation and the apparent growth rate due to coagulation scavenging by larger particles. These formulae were used on a set of simulations covering a wide range of atmospheric conditions. The modal growth rates were determined from the simulation results by summing the contribution of each process, by calculating the increase rate in the count mean diameter of the mode and by following the peak concentration of the mode. The results of these three methods were compared with each other and the means used to estimate the growth rate due to self-coagulation and coagulation scavenging were found to give accurate values. We also investigated the role of charged particles and electric interactions in the growth of a nucleation mode. Charged particles were found to increase the growth rate due to both self-coagulation and coagulation scavenging by a factor of ~1.5 to 2. In case of increased condensation onto charged particles, the total condensational growth rate of a nucleation mode may increase significantly in the very early steps of the growth. The analytical formulae provided by this paper were designed to provide the growth rates due to different processes from aerosol dynamic simulations, but the same principles can be used to determine the growth rates from measurement data.
Coherence of long-term stratospheric ozone vertical distribution time series used for the study of ozone recovery at a northern mid-latitude station

The coherence of stratospheric ozone time series retrieved from various observational records is investigated at Haute-Provence Observatory (OHP–43.93° N, 5.71° E). The analysis is accomplished through the intercomparison of collocated ozone measurements of Light Detection and Ranging (lidar) with Solar Backscatter UltraViolet(/2) (SBUV(/2)), Stratospheric Aerosol and Gas Experiment II (SAGE~II), Halogen Occultation Experiment (HALOE), Microwave Limb Sounder (MLS) on Upper Atmosphere Research Satellite (UARS) and Aura and Global Ozone Monitoring by Occultation of Stars (GOMOS) satellite observations as well as with in situ ozonesondes and ground-based Umkehr measurements performed at OHP. A detailed statistical study of the relative differences of ozone observations over the whole stratosphere is performed to detect any specific drift in the data. On average, all instruments show their best agreement with lidar at 20–40 km, where deviations are within ±5 %. Discrepancies are somewhat higher below 20 and above 40 km. The agreement with SAGE II data is remarkable since average differences are within ±1 % at 17–41 km. In contrast, Umkehr data underestimate systematically the lidar measurements in the whole stratosphere with a near zero bias at 16–8 hPa (~30 km). Drifts are estimated using simple linear regression for the data sets analysed in this study, from the monthly averaged difference time series. The derived values are less than ±0.5 % yr−1 in the 20–40 km altitude range and most drifts are not significant at the 2σ level. We also discuss the possibilities of extending the SAGE II and HALOE data with the GOMOS and Aura MLS data in consideration with relative offsets and drifts since the combination of such data sets are likely to be used for the study of stratospheric ozone recovery in the future.
Large-scale and synoptic meteorology in the south-east Pacific during the observations campaign VOCALS-REx in austral Spring 2008

We present a descriptive overview of the meteorology in the south eastern subtropical Pacific (SEP) during the VOCALS-REx intensive observations campaign which was carried out between October and November 2008. Mainly based on data from operational analyses, forecasts, reanalysis, and satellite observations, we focus on spatio-temporal scales from synoptic to planetary. A climatological context is given within which the specific conditions observed during the campaign are placed, with particular reference to the relationships between the large-scale and the regional circulations. The mean circulations associated with the diurnal breeze systems are also discussed. We then provide a summary of the day-to-day synoptic-scale circulation, air-parcel trajectories, and cloud cover in the SEP during VOCALS-REx. Three meteorologically distinct periods of time are identified and the large-scale causes for their different character are discussed. The first period was characterised by significant variability associated with synoptic-scale systems interesting the SEP; while the two subsequent phases were affected by planetary-scale disturbances with a slower evolution. The changes between initial and later periods can be partly explained from the regular march of the annual cycle, but contributions from subseasonal variability and its teleconnections were important. Across the whole of the two months under consideration we find a significant correlation between the depth of the inversion-capped marine boundary layer (MBL) and the amount of low cloud in the area of study. We discuss this correlation and argue that at least as a crude approximation a typical scaling may be applied relating MBL and cloud properties with the large-scale parameters of SSTs and tropospheric temperatures. These results are consistent with previously found empirical relationships involving lower-tropospheric stability.