Items

Advanced search

Observations of planetary waves in the mesosphere-lower thermosphere during stratospheric warming events

This study investigates the effect of stratospheric sudden warmings (SSWs) on planetary wave (PW) activity in the mesosphere–lower thermosphere (MLT). PW activity near 95 km is derived from meteor wind data using a chain of eight SuperDARN radars at high northern latitudes that span longitudes from 150° W to 25° E and latitudes from 51 to 66° N. Zonal wave number 1 and 2 components were extracted from the meridional wind for the years 2000–2008. The observed wintertime PW activity shows common features associated with the stratospheric wind reversals and the accompanying stratospheric warming events. Onset dates for seven SSW events accompanied by an elevated stratopause (ES) were identified during this time period using the Specified Dynamics Whole Atmosphere Community Climate Model (SD-WACCM). For the seven events, a significant enhancement in wave number 1 and 2 PW amplitudes near 95 km was found to occur after the wind reversed at 50 km, with amplitudes maximizing approximately 5 days after the onset of the wind reversal. This PW enhancement in the MLT after the event was confirmed using SD-WACCM. When all cases of polar cap wind reversals at 50 km were considered, a significant, albeit moderate, correlation of 0.4 was found between PW amplitudes near 95 km and westward polar-cap stratospheric winds at 50 km, with the maximum correlation occurring &sim; 3 days after the maximum westward wind. These results indicate that the enhancement of PW amplitudes near 95 km is a common feature of SSWs irrespective of the strength of the wind reversal.
Lidar profiling of aerosol optical properties from Paris to Lake Baikal (Siberia)

In June 2013, a ground-based mobile lidar performed the ~10 000 km ride from Paris to Ulan-Ude, near Lake Baikal, profiling for the first time aerosol optical properties all the way from western Europe to central Siberia. The instrument was equipped with N2-Raman and depolarization channels that enabled an optical speciation of aerosols in the low and middle troposphere. The extinction-to-backscatter ratio (also called lidar ratio or LR) and particle depolarization ratio (PDR) at 355 nm have been retrieved. The LR in the lower boundary layer (300–700 m) was found to be 63 ± 17 sr on average during the campaign with a distribution slightly skewed toward higher values that peaks between 50 and 55 sr. Although the difference is small, PDR values observed in Russian cities (>2%, except after rain) are systematically higher than the ones measured in Europe (<1%), which is probably an effect of the lifting of terrigenous aerosols by traffic on roads. Biomass burning layers from grassland or/and forest fires in southern Russia exhibit LR values ranging from 65 to 107 sr and from 3 to 4% for the PDR. During the route, desert dust aerosols originating from the Caspian and Aral seas regions were characterized for the first time, with a LR (PDR) of 43 ± 14 sr (23 ± 2%) for pure dust. The lidar observations also showed that this dust event extended over 2300 km and lasted for ~6 days. Measurements from the Moderate Resolution Imaging Spectrometer (MODIS) show that our results are comparable in terms of aerosol optical thickness (between 0.05 and 0.40 at 355 nm) with the mean aerosol load encountered throughout our route.
Airborne determination of the temporo-spatial distribution of benzene, toluene, nitrogen oxides and ozone in the boundary layer across Greater London, UK

Highly spatially resolved mixing ratios of benzene and toluene, nitrogen oxides (NOx) and ozone (O3) were measured in the atmospheric boundary layer above Greater London during the period 24 June to 9 July 2013 using a Dornier 228 aircraft. Toluene and benzene were determined in situ using a proton transfer reaction mass spectrometer (PTR-MS), NOx by dual-channel NOx chemiluminescence and O3 mixing ratios by UV absorption. Average mixing ratios observed over inner London at 360 ± 10 m a.g.l. were 0.20 ± 0.05, 0.28 ± 0.07, 13.2 ± 8.6, 21.0 ± 7.3 and 34.3 ± 15.2 ppbv for benzene, toluene, NO, NO2 and NOx respectively. Linear regression analysis between NO2, benzene and toluene mixing ratios yields a strong covariance, indicating that these compounds predominantly share the same or co-located sources within the city. Average mixing ratios measured at 360 ± 10 m a.g.l. over outer London were always lower than over inner London. Where traffic densities were highest, the toluene / benzene (T / B) concentration ratios were highest (average of 1.8 ± 0.5 ppbv ppbv-1), indicative of strong local sources. Daytime maxima in NOx, benzene and toluene mixing ratios were observed in the morning (~ 40 ppbv NOx, ~ 350 pptv toluene and ~ 200 pptv benzene) and in the mid-afternoon for ozone (~ 40 ppbv O3), all at 360 ± 10 m a.g.l.
Chemical composition and size distribution of summertime PM2.5 at a high altitude remote location in the northeast of the Qinghai–Xizang (Tibet) Plateau: insights into aerosol sources and processing in free troposphere

Aerosol filter samples were collected at a high-elevation mountain observatory (4180 m a.s.l.) in the northeastern part of the Qinghai–Xizang (Tibet) Plateau (QXP) during summer 2012 using a low-volume sampler and a micro-orifice uniform deposit impactor (MOUDI). These samples were analyzed for water-soluble inorganic ions (WSIs), organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and total organic nitrogen (TON) to elucidate the size-resolved chemical composition of free tropospheric aerosols in the QXP region. The average mass concentration of the sum of the analyzed species in PM2.5 (particle matter) (WSIs + OC + EC + TON) was 3.74 μg sm−3, 36% of which was sulfate, 18% OC, 17 % nitrate, 10% ammonium, 6.6% calcium, 6.4% TON, 2.6% EC, 1.5 % sodium, 0.9% chloride, 0.5% magnesium, and 0.3% potassium. The size distributions of sulfate and ammonium peaked in the accumulation mode (0.32–0.56 μm), whereas the size distributions of both nitrate and calcium peaked in the range of 1.8–3.2 μm, suggesting the formation of nitrate on mineral dust. OC, EC and TON were also predominantly found in the accumulation mode. The bulk chemical composition and the average oxidation degree of water-soluble organic matter (WSOM) were assessed using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). WSOM was found to be highly oxidized in all PM2.5 samples with an average oxygen-to-carbon atomic ratio (O / C) of 1.16 and an organic mass-to-organic carbon ratio (OM / OC) of 2.75. The highly oxidized WSOM was likely related to active cloud processing during upslope air mass transport coupled with strongly oxidizing environments caused by snow/ice photochemistry. High average ratios of OC / EC (7.6) and WSOC / OC (0.79) suggested that organic aerosols were primarily made of secondary species. Secondary organic aerosol (SOA) was estimated on average accounting for 80% (62–96%) of the PM2.5, indicating that SOA is an important component of free tropospheric aerosols over the northern QXP.
Molecular characterization of free tropospheric aerosol collected at the Pico Mountain Observatory: a case study with a long-range transported biomass burning plume

Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m−3. On average, organic aerosol components represent the largest mass fraction of the total measured aerosol (60 ± 51%), followed by sulfate (23 ± 28%), nitrate (13 ± 10%), chloride (2 ± 3%), and elemental carbon (2 ± 2%). Water-soluble organic matter (WSOM) extracted from two aerosol samples (9/24 and 9/25) collected consecutively during a pollution event were analyzed using ultrahigh-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Approximately 4000 molecular formulas were assigned to each of the mass spectra in the range of m/z 100–1000. The majority of the assigned molecular formulas had unsaturated structures with CHO and CHNO elemental compositions. FLEXPART retroplume analyses showed the sampled air masses were very aged (average plume age > 12 days). These aged aerosol WSOM compounds had an average O/C ratio of ~ 0.45, which is relatively low compared to O/C ratios of other aged aerosol. The increase in aerosol loading during the measurement period of 9/24 was linked to biomass burning emissions from North America by FLEXPART retroplume analysis and Moderate Resolution Imaging Spectroradiometer (MODIS) fire counts. This was confirmed with biomass burning markers detected in the WSOM and with the morphology and mixing state of particles as determined by scanning electron microscopy. The presence of markers characteristic of aqueous-phase reactions of phenolic species suggests that the aerosol collected at the Pico Mountain Observatory had undergone cloud processing before reaching the site. Finally, the air masses of 9/25 were more aged and influenced by marine emissions, as indicated by the presence of organosulfates and other species characteristic of marine aerosol. The change in the air masses for the two samples was corroborated by the changes in ethane, propane, and ozone, morphology of particles, as well as by the FLEXPART retroplume simulations. This paper presents the first detailed molecular characterization of free tropospheric aged aerosol intercepted at a lower free troposphere remote location and provides evidence of low oxygenation after long-range transport. We hypothesize this is a result of the selective removal of highly aged and polar species during long-range transport, because the aerosol underwent a combination of atmospheric processes during transport facilitating aqueous-phase removal (e.g., clouds processing) and fragmentation (e.g., photolysis) of components.
Influence of particle-phase state on the hygroscopic behavior of mixed organic–inorganic aerosols

Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle-phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids to phase-separated particles to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40 to 90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids; (2) forcing a single phase but accounting for non-ideal interactions through activity coefficient calculations; and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation of the inorganic and organic components is assumed at all RH values, with water uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that no single simplified modeling approach can be used to capture the water-uptake behavior for the diversity of particle-phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to produce substantial errors in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.
Signatures of the 2-day wave and sudden stratospheric warmings in Arctic water vapour observed by ground-based microwave radiometry

The ground-based microwave radiometer MIAWARA-C recorded the upper stratospheric and lower mesospheric water vapour distribution continuously from June 2011 to March 2013 above the Arctic station of Sodankylä, Finland (67.4° N, 26.6° E) without major interruptions and offers water vapour profiles with temporal resolution of 1 h for average conditions. The water vapour time series of MIAWARA-C shows strong periodic variations in both summer and winter related to the quasi-2-day wave. Above 0.1 hPa the amplitudes are strongest in summer. The stratospheric wintertime 2-day wave is pronounced for both winters on altitudes below 0.1 hPa and reaches a maximum amplitude of 0.8 ppmv in November 2011. Over the measurement period, the instrument monitored the changes in water vapour linked to two sudden stratospheric warmings in early 2012 and 2013. Based on the water vapour measurements, the descent rate in the vortex after the warmings is 364 m d−1 for 2012 and 315 m d−1 for 2013.
Ozone distributions over southern Lake Michigan: comparisons between ferry-based observations, shoreline-based DOAS observations and model forecasts

Air quality forecast models typically predict large summertime ozone abundances over water relative to land in the Great Lakes region. While each state bordering Lake Michigan has dedicated monitoring systems, offshore measurements have been sparse, mainly executed through specific short-term campaigns. This study examines ozone abundances over Lake Michigan as measured on the Lake Express ferry, by shoreline differential optical absorption spectroscopy (DOAS) observations in southeastern Wisconsin and as predicted by the Community Multiscale Air Quality (CMAQ) model. From 2008 to 2009 measurements of O3, SO2, NO2 and formaldehyde were made in the summertime by DOAS at a shoreline site in Kenosha, WI. From 2008 to 2010 measurements of ambient ozone were conducted on the Lake Express, a high-speed ferry that travels between Milwaukee, WI, and Muskegon, MI, up to six times daily from spring to fall. Ferry ozone observations over Lake Michigan were an average of 3.8 ppb higher than those measured at shoreline in Kenosha, with little dependence on position of the ferry or temperature and with greatest differences during evening and night. Concurrent 1–48 h forecasts from the CMAQ model in the upper Midwestern region surrounding Lake Michigan were compared to ferry ozone measurements, shoreline DOAS measurements and Environmental Protection Agency (EPA) station measurements. The bias of the model O3 forecast was computed and evaluated with respect to ferry-based measurements. Trends in the bias with respect to location and time of day were explored showing non-uniformity in model bias over the lake. Model ozone bias was consistently high over the lake in comparison to land-based measurements, with highest biases for 25–48 h after initialization.
Influence of isoprene chemical mechanism on modelled changes in tropospheric ozone due to climate and land use over the 21st century

Isoprene is a~precursor to tropospheric ozone, a key pollutant and greenhouse gas. Anthropogenic activity over the coming century is likely to cause large changes in atmospheric CO2 levels, climate and land use, all of which will alter the global vegetation distribution leading to changes in isoprene emissions. Previous studies have used global chemistry–climate models to assess how possible changes in climate and land use could affect isoprene emissions and hence tropospheric ozone. The chemistry of isoprene oxidation, which can alter the concentration of ozone, is highly complex, therefore it must be parameterised in these models. In this work, we compare the effect of four different reduced isoprene chemical mechanisms, all currently used in Earth system models, on tropospheric ozone. Using a box model we compare ozone in these reduced schemes to that in a more explicit scheme (the Master Chemical Mechanism) over a range of NOx and isoprene emissions, through the use of O3 isopleths. We find that there is some variability, especially at high isoprene emissions, caused by differences in isoprene-derived NOx reservoir species. A global model is then used to examine how the different reduced schemes respond to potential future changes in climate, isoprene emissions, anthropogenic emissions and land use change. We find that, particularly in isoprene-rich regions, the response of the schemes varies considerably. The wide-ranging response is due to differences in the model descriptions of the peroxy radical chemistry, particularly their relative rates of reaction towards NO, leading to ozone formation, or HO2, leading to termination. Also important is the yield of isoprene nitrates and peroxyacyl nitrate precursors from isoprene oxidation. Those schemes that produce less of these NOx reservoir species, tend to produce more ozone locally and less away from the source region. We also note changes in other key oxidants such as NO3 and OH (due to the inclusion of additional isoprene-derived HOx recycling pathways). These have implications for secondary organic aerosol formation, as does the inclusion of an epoxide formation pathway in one of the mechanisms. By combining the emissions and O3 data from all of the global model integrations, we are able to construct isopleth plots comparable to those from the box model analysis. We find that the global and box model isopleths show good qualitative agreement, suggesting that comparing chemical mechanisms with a box model in this framework is a useful tool for assessing mechanistic performance in complex global models. We conclude that as the choice of reduced isoprene mechanism may alter both the magnitude and sign of the ozone response, how isoprene chemistry is parameterised in perturbation experiments such as these is a crucially important consideration. More measurements and laboratory studies are needed to validate these reduced mechanisms especially under high-volatile-organic-compound, low-NOx conditions.
Modeling organic aerosol composition at the puy de Dôme mountain (France) for two contrasted air masses with the WRF-Chem model

Simulations with the chemistry-transport model WRF-Chem are compared to aerosol measurements performed at the puy de Dôme station with a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS) for two episodes in autumn 2008 and in summer 2010. The WRF-Chem model is used with the Volatility Basis Set (VBS) approach dedicated to the formation of secondary organic aerosol (SOA). The model systematically underestimates the observed concentrations of organic aerosol (OA), with significant differences observed for the summer case. For this event, where high OA concentrations were observed (12.5 μg m-3 in average), simulated OA mass concentration is 2.0 μg m-3. For the autumn event, observed OA concentrations reached 2.6 μg m-3. The simulated concentrations reached only 0.6 μg m-3. During the summer event, several gas-phase volatile organic compounds (VOCs) were measured and were used to test the robustness of both emission/dry deposition and SOA formation processes. The concentrations of VOCs, and more specifically the anthropogenic ones, calculated by the model are estimated to be much lower than the observed ones. Hence, the emissions of all SOA precursors are multiplied by 2 in the model: this induces an increase of the mean OA mass concentration of 25% (+0.5 μg m-3) and 18% (+0.4 μg m-3), respectively for anthropogenic and biogenic VOCs. The dry deposition of gas-phase organic condensable vapours (OCVs) is also critical to predict the SOA mass concentrations: dividing the deposition factor by 2 leads to an increase of OA mass by an additional 12% (+0.2 μg m-3). However, these increases were not sufficient to explain the observed OA concentration, and the underestimation of the OA concentration levels seems to be principally related to a lack in the parameterization of SOA formation. Changing the oxidation rate of OCVs from 1.0 × 10-11 to 4.0 × 10-11 cm3 molecule−1 s-1, doubling the SOA yields for anthropogenic VOCs and finally doubling the SOA yields for biogenic VOCs results in an increase of the mean OA mass concentration by 56% (+1.1 μg m-3), 61% (+1.2 μg m-3) and 40% (+0.8 μg m-3), respectively. The consideration of both emission/dry deposition and SOA formation processes tests lead to a mean OA mass concentration of 10.7 μg m-3 for 2010, a value that is close to the observations. For 2008, modifying solely the oxidation rate of OCVs and the SOA yields is sufficient to reproduce the observed level of mean OA mass (a mass of 2.4 μg m-3 is obtained by the model whereas a mass of 2.6 μg m-3 was observed).