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A Polar Stratospheric Cloud (PSC) was detected for the first time in January 2006 over Southern Europe after 25 years of systematic lidar observations. This cloud was observed while the polar vortex was highly distorted during the initial phase of a major stratospheric warming. Very cold stratospheric temperatures (<190 K) centred over the Northern-Western Europe were reported, extending down to the South of France where lidar observations were performed. CTM (Chemical Transport Model) investigations show that this event led to a significant direct ozone destruction (35 ppb/day), within and outside the vortex as chlorine activated air masses were moved to sunlight regions allowing ozone destruction. If such exceptional events of mid-latitudes PSCs were to become frequent in the future, they should not compromise the ozone recovery because their effect appears to be limited temporally and spatially. More importantly, these events might tend to be associated with the initial phase of a stratospheric warming that results into a weakening and warming of the polar vortex and hence into a reduced probability occurrence of PSC temperatures during the rest of the winter.
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This study presents a new method, Köhler Theory Analysis (KTA), to infer the molar volume and solubility of organic aerosol constituents. The method is based on measurements of surface tension, chemical composition, and CCN activity coupled with Köhler theory. KTA is evaluated by inferring the molar volume of six known organics (four dicarboxylic acids, one amino acid, and one sugar) in pure form and in mixtures with ammonium sulfate ((NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>). The average error in inferred molar volumes are to within 18% of their expected value for organic fractions between 50 and 90%. This suggests that KTA is a potentially powerful tool for determining the CCN characteristic of ambient water soluble organic carbon (WSOC), providing physically-based constraints for aerosol-cloud interaction parameterizations.
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We have examined the 532-nm aerosol backscatter coefficient measurements by the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) for their use in the monitoring of stratospheric aerosol. CALIPSO makes observations that span from 82° S to 82° N each day and, for each profile, backscatter coefficient values reported up to ~40 km. The possibility of using CALIPSO for stratospheric aerosol monitoring is demonstrated by the clear observation of the 20 May 2006 eruption of Montserrat in the earliest CALIPSO data in early June as well as by observations showing the 7 October 2006 eruption of Tavurvur (Rabaul). However, the very low aerosol loading within the stratosphere makes routine observations of the stratospheric aerosol far more difficult than relatively dense volcanic plumes. Nonetheless, we found that averaging a complete days worth of nighttime-only data into 5-deg latitude by 1-km vertical bins yields a stratospheric aerosol distribution that is fairly consistent with past measurements by spaceborne instruments. Based on comparisons with 2004 data from the Stratospheric Aerosol and Gas Experiment, the derived values are close to expectation except in the tropics where they are larger by about a factor of 2. The cause of the difference in the tropics is not readily apparent but is most likely related to difficulties in the lidar calibration process currently found in the CALIOP data at tropical latitudes.
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We present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer (BL) and the free troposphere (FT) and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (<I>r</I><sup>2</sup>=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally <1% of PAN. Diurnal cycles and relationships of APNs with ozone reveal a gradient in hydrocarbon chemistry between the BL and the FT. On average, levels of APNs, ozone and PPN/PAN are substantially higher in FT air relative to BL air, suggesting that this site is strongly influenced by distant pollution sources. To estimate the impact of long-range transport of Asian pollution on atmospheric composition at MBO, we perform a detailed analysis utilizing HYSPLIT back trajectories. This analysis suggests that trans-Pacific transport of Asian pollution leads to substantial increases in APN and ozone mixing ratios at MBO, especially when transport occurs via the free troposphere. The ensemble of trajectories indicate that Asian-influenced free tropospheric air was sampled in ~16% of our data and contained a median PAN mixing ratio double that of the full dataset.
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Day-of-week patterns in human activities can be used to examine the ways in which differences in primary emissions result in changes in the rates of photochemical reactions, and the production of secondary pollutants. Data from twelve California Air Resources Board monitoring sites in Sacramento, CA, and the downwind Mountain Counties air basin are analyzed to reveal day of week patterns in ozone and its precursors in the summers of 1998–2002. Measurements of non-methane hydrocarbons are available for the summers of 2001–2003 at three of these sites and NO<sub>x</sub> at six of these sites for the full time period. This routine monitoring data is complemented by data sets of ozone and nitrogen oxide concentrations obtained in the summers of 2001 and 2003 at three sites in the region and comprehensive measurements of VOC reactivity at two sites in 2001. Daytime concentrations of nitrogen oxides (NO<sub>x</sub>≡NO+NO<sub>2</sub>) are approximately 35% lower on weekends at all the sites, whereas the VOC reactivity changes by less than 10%. All six sites in the Sacramento Valley have higher 8-h maximum average ozone on the weekend and are more likely to exceed the national standard of 85 ppb on the weekend. In contrast, all the sites in the Mountain Counties are less likely to exceed the federal ozone standard on the weekend. Analysis of the day-of-week trends in odd oxygen show that the weekend effect of ozone within Sacramento is strongly influenced by NO sources close to the monitoring sites. This suggests that ozone measurements from monitoring sites close to highways, including two rural locations, may not be representative of the regional abundance, and lead to underestimates of long term exposure for humans and ecosystems.
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Interest in the potential formation of secondary organic aerosol (SOA) through reactions of organic compounds in condensed aqueous phases is growing. In this study, the potential formation of SOA from irreversible aqueous-phase reactions of organic species in clouds was investigated. A new proposed aqueous-phase chemistry mechanism (AqChem) is coupled with the existing gas-phase Caltech Atmospheric Chemistry Mechanism (CACM) and the Model to Predict the Multiphase Partitioning of Organics (MPMPO) that simulate SOA formation. AqChem treats irreversible organic reactions that lead mainly to the formation of carboxylic acids, which are usually less volatile than the corresponding aldehydic compounds. Zero-dimensional model simulations were performed for tropospheric conditions with clouds present for three consecutive hours per day. Zero-dimensional model simulations show that 48-h average SOA formation is increased by 27% for a rural scenario with strong monoterpene emissions and 7% for an urban scenario with strong emissions of aromatic compounds, respectively, when irreversible organic reactions in clouds are considered. AqChem was also incorporated into the Community Multiscale Air Quality Model (CMAQ) version 4.4 with CACM/MPMPO and applied to a previously studied photochemical episode (3–4 August 2004) focusing on the eastern United States. The CMAQ study indicates that the maximum contribution of SOA formation from irreversible reactions of organics in clouds is 0.28 μg m<sup>−3</sup> for 24-h average concentrations and 0.60 μg m<sup>−3</sup> for one-hour average concentrations at certain locations. On average, domain-wide surface SOA predictions for the episode are increased by 9% when irreversible, in-cloud processing of organics is considered. Because aldehydes of carbon number greater than four are assumed to convert fully to the corresponding carboxylic acids upon reaction with OH in cloud droplets and this assumption may overestimate carboxylic acid formation from this reaction route, the present study provides an upper bound estimate of SOA formation via this pathway.
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The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO<sub>2</sub> radicals with the Fluorescence Assay by Gas Expansion (FAGE) technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC) instrument and a GC instrument for formaldehyde detection; NO/NO<sub>2</sub>, CO, O<sub>3</sub>, and H<sub>2</sub>O vapour analysers. Ray tracing simulations and NO<sub>2</sub> actinometry have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O<sub>3</sub> and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1) high precision kinetics investigations over a range of atmospheric conditions; (2) detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3) field instrument intercomparison, calibration, development, and investigations of instrument response at a range of atmospheric conditions.
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A meso-scale model was used to understand and describe the dynamical processes driving high ozone concentrations observed during both dry and monsoon season in monthly climatologies profiles over Lagos (Nigeria, 6.6° N, 3.3° E), obtained with the MOZAIC airborne measurements (ozone and carbon monoxide). This study focuses on ozone enhancements observed in the upper-part of the lower troposphere, around 3000 m. Two individual cases have been selected in the MOZAIC dataset as being representative of the climatological ozone enhancements, to be simulated and analyzed with on-line Lagrangian backtracking of air masses. <br><br> This study points out the role of baroclinic low-level circulations present in the Inter Tropical Front (ITF) area. Two low-level thermal cells around a zonal axis and below 2000 m, in mirror symmetry to each other with respect to equator, form near 20° E and around 5° N and 5° S during the (northern hemisphere) dry and wet seasons respectively. They are caused by surface gradients – the warm dry surface being located poleward of the ITF and the cooler wet surface equatorward of the ITF. <br><br> A convergence line exists between the poleward low-level branch of each thermal cell and the equatorward low-level branch of the Hadley cell. Our main conclusion is to point out this line as a preferred location for fire products – among them ozone precursors – to be uplifted and injected into the lower free troposphere. <br><br> The free tropospheric transport that occurs then depends on the hemisphere and season. In the NH dry season, the AEJ allows transport of ozone and precursors westward to Lagos. In the NH monsoon (wet) season, fire products are transported from the southern hemisphere to Lagos by the southeasterly trade that surmounts the monsoon layer. Additionally ozone precursors uplifted by wet convection in the ITCZ can also mix to the ones uplifted by the baroclinic cell and be advected up to Lagos by the trade flow.
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We introduce the improved Freie Universität Berlin (FUB) high-resolution radiation scheme FUBRad and compare it to the 4-band standard ECHAM5 SW radiation scheme of Fouquart and Bonnel (FB). Both schemes are validated against the detailed radiative transfer model libRadtran. FUBRad produces realistic heating rate variations during the solar cycle. The SW heating rate response with the FB scheme is about 20 times smaller than with FUBRad and cannot produce the observed temperature signal. A reduction of the spectral resolution to 6 bands for solar irradiance and ozone absorption cross sections leads to a degradation (reduction) of the solar SW heating rate signal by about 20%. <br><br> The simulated temperature response agrees qualitatively well with observations in the summer upper stratosphere and mesosphere where irradiance variations dominate the signal. <br><br> Comparison of the total short-wave heating rates under solar minimum conditions shows good agreement between FUBRad, FB and libRadtran up to the middle mesosphere (60–70 km) indicating that both parameterizations are well suited for climate integrations that do not take solar variability into account. <br><br> The FUBRad scheme has been implemented as a sub-submodel of the Modular Earth Submodel System (MESSy).
