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Global distributions of nitric acid from IASI/MetOP measurements

This paper presents the first global distributions of HNO3 total columns acquired by the Infrared Atmospheric Sounding Interferometer (IASI) instrument, launched onboard the MetOp platform in October 2006. IASI is an infrared nadir-looking Fourier transform spectrometer providing atmospheric radiance spectra at 0.5 cm−1 spectral resolution, from which temperature and infrared absorbing gas concentration profiles are retrieved with global Earth coverage twice a day. A first analysis of the IASI measurements in terms of information content demonstrates the possibility of retrieving a total column for HNO3 at all latitudes with a maximal sensitivity in the middle stratosphere. The retrievals are performed from IASI spectra in the atmospheric window using a fast radiative transfer model and inversion software (FORLI) relying on the Optimal Estimation Method. The operational processing of HNO3 total columns is achieved since March 2008. We show that FORLI-HNO3 performs well at all latitudes (RMS of the spectral residuals around 2.3×10−6 W/m2 sr m−1) and provides HNO3 total columns with on average statistical errors of about 12%, reaching the threshold value of 32% at the equatorial belt. The global distributions of the retrieved total columns for one year (from March 2008 to February 2009) are presented and discussed with emphasis given to seasonal and interhemispheric variations. Local seasonal variations at 6 specific locations are also described and discussed in comparison with MLS volume mixing ratios at 46.5 hPa. The seasonal cycle observed in Polar regions is highlighted, with maxima observed in fall-winter and minima during spring-summer. The denitrification inside the Antarctic polar vortex during winter is clearly revealed with unprecedented horizontal resolution: HNO3 columns decreasing down to about 1×1016 molecules cm−2 are observed, which is consistent with the lower values of temperature observed between 50 and 15 hPa (~20–25 km) and the resulting formation and sedimentation of polar stratospheric clouds. During the same period, the collar region of high quantities of HNO3 at the vortex edge is also observed around 65–60° S latitude. Preliminary correlations between IASI derived HNO3 and O3 columns inside the polar vortex are presented and discussed.
Technical Note: A SAGE-corrected SBUV zonal-mean ozone data set

A stratospheric vertically resolved, monthly, zonal-mean ozone data set based on Satellite Aerosol and Gas Experiment (SAGE) and Solar Backscatter UltraViolet (SBUV) data spanning 1979–2005 is presented. Drifts in individual SBUV instruments and inter-SBUV biases are corrected using SAGE I and II by calculating differences between coincident SAGE-SBUV measurements. In this way the daily, near-global coverage of SBUV(/2) is combined with the stability and precision of SAGE to provide a homogeneous ozone record suitable for trend analysis. The resultant SAGE-corrected SBUV data set, shows, for example, a more realistic Quasi-Biennial Oscillation signal compared to the one derived from SBUV data alone. Furthermore, this methodology can be used to extend the present data set beyond the lifetime of SAGE II.
Kinetic modeling of nucleation experiments involving SO2 and OH: new insights into the underlying nucleation mechanisms

Nucleation is an important source of atmospheric aerosols which have significant climatic and health implications. Despite intensive theoretical and field studies over the past decades, the dominant nucleation mechanism in the lower troposphere remains to be mysterious. Several recent laboratory studies on atmospheric nucleation may shed light on this important problem. However, the most interesting finding from those studies was based on the derived H2SO4 concentration whose accuracy has not yet been evaluated by any other means. Moreover, the threshold H2SO4 concentration needed to reach the same degree of nucleation reported by two separate nucleation studies varies by about one order of magnitude. In this study, we apply a recently updated kinetic nucleation model to study the nucleation phenomena observed in those recent experiments. We show that the H2SO4 concentration can be estimated with a higher level of accuracy with the kinetic model by constraining the simulated particle size distributions with observed ones. We find that the required H2SO4 concentrations to achieve the best agreement between modeling and measurements are a factor of ~2 to 4 higher than reported in those experiments. More importantly, by comparing the derived thermodynamic properties associated with the nucleation process, we conclude that different unknown species may participate in the two separate nucleation experimental studies, which may explain the large difference in the reported threshold H2SO4 concentration. Although the unknown species involved has yet to be identified, the derived values of thermodynamic properties can serve as a valuable guideline for the search of their chemical identities using advanced quantum-chemical approaches.
Technical Note: Formal blind intercomparison of OH measurements: results from the international campaign HOxComp

Hydroxyl radicals (OH) are the major oxidizing species in the troposphere. Because of their central importance, absolute measurements of their concentrations are needed to validate chemical mechanisms of atmospheric models. The extremely low and highly variable concentrations in the troposphere, however, make measurements of OH difficult. Three techniques are currently used worldwide for tropospheric observations of OH after about 30~years of technical developments: Differential Optical Laser Absorption Spectroscopy (DOAS), Laser-Induced Fluorescence Spectroscopy (LIF), and Chemical Ionisation Mass Spectrometry (CIMS). Even though many measurement campaigns with OH data were published, the question of accuracy and precision is still under discussion. Here, we report results of the first formal, blind intercomparison of these techniques. Six OH instruments (4~LIF, 1~CIMS, 1~DOAS) participated successfully in the ground-based, international HOxComp campaign carried out in Jülich, Germany, in summer 2005. Comparisons were performed for three days in ambient air (3~LIF, 1 CIMS) and for six days in the atmosphere simulation chamber SAPHIR (3~LIF, 1~DOAS). All instruments were found to measure tropospheric OH concentrations with high sensitivity and good time resolution. The pairwise correlations between different data sets were linear and yielded high correlation coefficients (r2=0.75−0.96). Excellent absolute agreement was observed for the instruments at the SAPHIR chamber, yielding slopes between 1.01 and 1.13 in the linear regressions. In ambient air, the slopes deviated from unity by factors of 1.06 to 1.69, which can partly be explained by the stated instrumental accuracies. In addition, sampling inhomogeneities and calibration problems have apparently contributed to the discrepancies. The absolute intercepts of the linear regressions did not exceed 0.6×106 cm−3, mostly being insignificant and of minor importance for daytime observations of OH. No relevant interferences with respect to ozone, water vapour, NOx and peroxy radicals could be detected. The HOxComp campaign has demonstrated that OH can be measured reasonably well by current instruments, but also that there is still room for improvement of calibrations.
Properties of the average distribution of equatorial Kelvin waves investigated with the GROGRAT ray tracer

Kelvin waves excited by tropospheric convection are considered to be one of the main drivers of the stratospheric quasi-biennial oscillation (QBO). In this paper we combine several measured data sets with the Gravity wave Regional Or Global RAy Tracer (GROGRAT) in order to study the forcing and vertical propagation of Kelvin waves. Launch distributions for the ray tracer at tropospheric altitudes are deduced from space-time spectra of European Centre for Medium-Range Weather Forecasts (ECMWF) operational analyses, as well as outgoing longwave radiation (OLR) and rainfall data measured by the Tropical Rainfall Measuring Mission (TRMM) satellite. The resulting stratospheric Kelvin wave spectra are compared to ECMWF operational analyses and temperature measurements of the Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) satellite instrument. Questions addressed are: the relative importance of source variability versus wind modulation, the relative importance of radiative and turbulent damping versus wave breaking, and the minimum altitude where freely propagating waves dominate the spectrum.
In situ aerosol optics in Reno, NV, USA during and after the summer 2008 California wildfires and the influence of absorbing and non-absorbing organic coatings on spectral light absorption

Hundreds of wildfires in Northern California were sparked by lightning during the summer of 2008, resulting in downwind smoke for the months of June and July. Comparisons are reported for aerosol optics measurements in Reno, Nevada made during the very smoky month of July and the relatively clean month of August. Photoacoustic instruments equipped with integrating nephelometers were used to measure aerosol light scattering and absorption coefficients at wavelengths of 405 nm and 870 nm, revealing a strong variation of aerosol light absorption with wavelength. Insight on fuels burned is gleaned from comparison of Ångström exponents of absorption (AEA) versus single scattering albedo (SSA) of the ambient measurements with laboratory biomass smoke measurements for many fuels. Measurements during the month of August, which were largely unaffected by fire smoke, exhibit surprisingly low AEA for aerosol light absorption when the SSA is highest, again likely as a consequence of the underappreciated wavelength dependence of aerosol light absorption by particles coated with non-absorbing organic and inorganic matter. Coated sphere calculations were used to show that AEA as large as 1.6 are possible for wood smoke even with non-absorbing organic coatings on black carbon cores, suggesting care be exercised when diagnosing AEA.
Global distribution of upper tropospheric formic acid from the ACE-FTS

We present the first near global upper tropospheric distribution of formic acid (HCOOH) observed from space using solar occultation measurements from the Fourier transform spectrometer (FTS) on board the Atmospheric Chemistry Experiment (ACE) satellite. Using a new set of spectroscopic line parameters recently published for formic acid by Vander Auwera et al. (2007) and Perrin and Vander Auwera (2007), we have retrieved the concentrations of HCOOH between 5 km and the tropopause for ACE-FTS observations from February 2004 to September 2007. We observe a significant seasonal dependence for the HCOOH concentrations related to vegetation growth and biomass burning. We estimate an emission ratio of 0.0051±0.0015 for HCOOH relative to CO for tropical South American fires using a selected set of data for September 2004. Results from the balloon-borne MkIV Fourier transform spectrometer are also presented and compared with the ACE measurements.
High levels of reactive gaseous mercury observed at a high elevation research laboratory in the Rocky Mountains

The chemical cycling and spatiotemporal distribution of mercury in the troposphere is poorly understood. We measured gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particulate mercury (HgP) along with carbon monoxide (CO), ozone (O3), aerosols, and meteorological variables at Storm Peak Laboratory at an elevation of 3200 m a.s.l., in Colorado, from 28 April to 1 July 2008. The mean mercury concentrations were 1.6 ng m−3 (GEM), 20 pg m−3 (RGM) and 9 pg m−3 (HgP). We observed eight events of strongly enhanced atmospheric RGM levels with maximum concentrations up to 137 pg m−3. RGM enhancement events lasted for long time periods of 2 to 6 days showing both enriched level during daytime and nighttime when other tracers (e.g., aerosols) showed different representations of boundary layer air and free tropospheric air. During seven of these events, RGM was inversely correlated to GEM (RGM/GEM regression slope ~−0.1), but did not exhibit correlations with ozone, carbon monoxide, or aerosol concentrations. Relative humidity was the dominant factor affecting RGM levels with high RGM levels always present whenever relative humidity was below 40 to 50%. We conclude that RGM enhancements observed at Storm Peak Laboratory were not induced by pollution events and were related to oxidation of tropospheric GEM. High RGM levels were not limited to upper tropospheric or stratospherically influenced air masses, indicating that entrainment processes and deep vertical mixing of free tropospheric air enriched in RGM may lead to high RGM levels throughout the troposphere and into the boundary layer over the Western United States. Based on backtrajectory analysis and a lack of mass balance between RGM and GEM, atmospheric production of RGM may also have occurred in some distance allowing for scavenging and/or deposition of RGM prior to reaching the laboratory. Our observations provide evidence that the tropospheric pool of mercury is frequently enriched in divalent mercury, that high RGM levels are not limited to upper tropospheric air masses, but that the build-up of high RGM in the troposphere is limited to the presence of dry air.
Vertical structure of aerosols and water vapor over West Africa during the African monsoon dry season

We present observations of tropospheric aerosol and water vapor transport over West Africa and the associated meteorological conditions during the AMMA SOP-0 dry season experiment, which was conducted in West Africa in January–February 2006. This study combines data from ultra-light aircraft (ULA)-based lidar, airborne in-situ aerosol and gas measurements, standard meteorological measurements, satellite-based aerosol measurements, airmass trajectories, and radiosonde measurements. At Niamey (13.5° N, 2.2° E) the prevailing surface wind (i.e. Harmattan) was from the northeast bringing dry dusty air from the Sahara desert. High concentrations of mineral dust aerosol were typically observed from the surface to 1.5 or 2 km associated with the Saharan airmasses. At higher altitudes the prevailing wind veered to the south or southeast bringing relatively warm and humid airmasses from the biomass burning regions to the Sahel (<10° N). These elevated layers had high concentrations of biomass burning aerosol and were typically observed between altitudes of 2–5 km. Meteorological analyses show these airmasses were advected upwards over the biomass burning regions through ascent in Inter-Tropical Discontinuity (ITD) zone. Aerosol vertical profiles obtained from the space-based lidar CALIOP onboard CALIPSO during January 2007 also showed the presence of dust particles (particle depolarization (δ)~30%, lidar Ångström exponent (LAE)<0, aerosol backscatter to extinction ratio (BER): 0.026~0.028 sr−1) at low levels (<1.5 km) and biomass burning smoke aerosol (δ<10%, LAE: 0.6~1.1, BER: 0.015~0.018 sr−1) between 2 and 5 km. CALIOP data indicated that these distinct continental dust and biomass burning aerosol layers likely mixed as they advected further south over the tropical Atlantic Ocean, as indicated an intermediate values of δ (10~17%), LAE (0.16~0.18) and BER (0.0021~0.0022 sr−1).
Using ground-based solar and lunar infrared spectroscopy to study the diurnal trend of carbon monoxide in the Mexico City boundary layer

Carbon monoxide (CO) is an important pollutant in urban agglomerations. Quantifying the total burden of this pollutant in a megacity is challenging because not only its surface concentration but also its vertical dispersion present different behaviours and high variability. The diurnal trend of columnar CO in the boundary layer of Mexico City has been measured during various days with ground-based infrared absorption spectroscopy. Daytime CO total columns are retrieved from solar spectra and for the first time, nocturnal CO total columns using moonlight have been retrieved within a megacity. The measurements were taken at the Universidad Nacional Autónoma de México (UNAM) campus located in Mexico City (19.33° N, 99.18° W, 2260 m a.s.l.) from October 2007 until February 2008 with a Fourier-transform infrared spectrometer at 0.5 cm−1 resolution. The atmospheric CO background column was measured from the high altitude site Altzomoni (19.12° N, 98.65° W, 4010 m a.s.l.) located 60 km southeast of Mexico City. The total CO column within the city presents large variations. Fresh CO emissions at the surface, the transport of cleaner or more polluted air masses within the field-of-view of the instrument and other processes contribute to this variability. The mean background value above the boundary mixing layer was found to be (8.4±0.5)×1017 molecules/cm2, while inside the city, the late morning mean on weekdays and Sundays was found to be (2.73±0.41)×1018 molecules/cm2 and (2.04±0.57)×1018 molecules/cm2, respectively. Continuous CO column retrieval during the day and night (when available), in conjunction with surface CO measurements, allow for a reconstruction of the effective mixing layer height. The limitations from this simplified approach, as well as the potential of using continuous column measurements in order to derive top-down CO emissions from a large urban area, are discussed. Also, further monitoring will provide more insight in daily and weekly emission patterns and a usable database for the quantitative validation of CO from satellite observations in a megacity.