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We introduce a method for deriving aerosol spectral radiative forcing along with single scattering albedo, asymmetry parameter, and surface albedo from airborne vertical profile measurements of shortwave spectral irradiance and spectral aerosol optical thickness. The new method complements the traditional, direct measurement of aerosol radiative forcing efficiency from horizontal flight legs below gradients of aerosol optical thickness, and is particularly useful over heterogeneous land surfaces and for homogeneous aerosol layers where the horizontal gradient method is impractical. Using data collected by the Solar Spectral Flux Radiometer (SSFR) and the Ames Airborne Tracking Sunphotometer (AATS-14) during the MILAGRO (Megacity Initiative: Local and Global Research Observations) experiment, we validate an over-ocean spectral aerosol forcing efficiency from the new method by comparing with the traditional method. Retrieved over-land aerosol optical properties are compared with in-situ measurements and AERONET retrievals. The spectral forcing efficiencies over ocean and land are remarkably similar and agree with results from other field experiments.
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Three different models for day-time atmospheric methanol, acetaldehyde, acetone, isoprene and monoterpene concentrations were developed using measurements above a boreal forest stand in Southern Finland in 2006–2007 and tested against an independent dataset from the same forest measured in summer 2008. The models were based on the exponential relationship between air temperature and the concentration of biogenic volatile organic compounds (BVOC). Our first model for BVOC concentrations was a simple exponential function of air temperature (T-model). The T-model could explain 27–66% of the variation of all the compounds, but it failed to catch the extremely high concentration peaks observed in summer. To improve the temperature model we developed two other models. The second model, a Temperature-State of Development- model (T-S model), included two explaining variables: air temperature and the seasonal photosynthetic efficiency. This model performed slightly better compared to the T-model for both datasets and increased the fraction of variation explained to 29–69%, but it still could not explain the high concentration peaks. To explain those we modified the T-S model to include environmental triggers that could increase the concentrations momentarily. The triggers that improved the model most were high photosynthetically active photon flux density (PPDF) compared to the seasonally available radiation and high ozone concentration. The Trigger model described the peak concentrations somewhat better than T or T-S model, thus the level of explanation was improved and was 30–71%. This study shows the importance to include seasonal variations in photosynthetic efficiency when modeling BVOC concentrations and presents the idea of a trigger model for explaining high peak concentrations of BVOCs. Our study suggests that when developing a trigger type modelfurther the model and the triggers should be more compounds-specific.
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The majority of tropospheric ozone depletion event (ODE) studies have focussed on time-series measurements, with comparatively few studies of the vertical component. Those that exist have almost exclusively used free-flying balloon-borne ozonesondes and almost all have been conducted in the Arctic. Here we use measurements from two separate Antarctic field experiments to examine the vertical profile of ozone during Antarctic ODEs. We use tethersonde data to probe details in the lowest few hundred meters and find considerable structure in the profiles associated with complex atmospheric layering. The profiles were all measured at wind speeds less than 7 ms<sup>−1</sup>, and on each occasion the lowest inversion height lay between 10 m and 40 m. We also use data from a free-flying ozonesonde study to select events where ozone depletion was recorded at altitudes >1 km above ground level. Using ERA-40 meteorological charts, we find that on every occasion the high altitude depletion was preceded by an atmospheric low pressure system. An examination of limited published ozonesonde data from other Antarctic stations shows this to be a consistent feature. Given the link between BrO and ODEs, we also examine ground-based and satellite BrO measurements and find a strong association between atmospheric low pressure systems and enhanced BrO that must arise in the troposphere. The results suggest that, in Antarctica, such depressions are responsible for driving high altitude ODEs and for generating the large-scale BrO clouds observed from satellites. In the Arctic, the prevailing meteorology differs from that in Antarctica, but, while a less common effect, major low pressure systems in the Arctic can also generate BrO clouds. Such depressions thus appear to be fundamental when considering the broader influence of ODEs, certainly in Antarctica, such as halogen export and the radiative influence of ozone-depleted air masses.
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Three interval constrained methods, including the interval constrained Kalman smoother, the interval constrained maximum likelihood ensemble smoother and the interval constrained ensemble Kalman smoother are developed to conduct inversions of atmospheric trace gas methane (CH<sub>4</sub>). The negative values of fluxes in an unconstrained inversion are avoided in the constrained inversion. In a multi-year inversion experiment using pseudo observations derived from a forward transport simulation with known fluxes, the interval constrained fixed-lag Kalman smoother presents the best results, followed by the interval constrained fixed-lag ensemble Kalman smoother and the interval constrained maximum likelihood ensemble Kalman smoother. Consistent uncertainties are obtained for the posterior fluxes with these three methods. This study provides alternatives of the variable transform method to deal with interval constraints in atmospheric inversions.
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In the last two decades, significant depletion of boundary layer ozone (ozone depletion events, ODEs) has been observed in both Arctic and Antarctic spring. ODEs are attributed to catalytic destruction by bromine radicals (Br plus BrO), especially during bromine explosion events (BEs), when high concentrations of BrO periodically occur. However, neither the exact source of bromine nor the mechanism for sustaining the observed high BrO concentrations is completely understood. Here, by considering the production of sea salt aerosol from snow lying on sea ice during blowing snow events and the subsequent release of bromine, we successfully simulate the BEs using a global chemistry transport model. We find that heterogeneous reactions play an important role in sustaining a high fraction of the total inorganic bromine as BrO. We also find that emissions of bromine associated with blowing snow contribute significantly to BrO at mid-latitudes. Modeled tropospheric BrO columns generally compare well with the tropospheric BrO columns retrieved from the GOME satellite instrument (Global Ozone Monitoring Experiment). The additional blowing snow bromine source, identified here, reduces modeled high latitude lower tropospheric ozone amounts by up to an average 8% in polar spring.
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For the first time, a comprehensive, height-resolved Doppler lidar study of updrafts and downdrafts in the mixing layer is presented. The Doppler lidar measurements were performed at Leipzig, Germany, in the summer half year of 2006. The conditional sampling method is applied to the measured vertical velocities to identify, count, and analyze significant updraft and downdraft events. Three cases of atmospheric boundary-layer (ABL) evolution with and without fair-weather cumuli formation are discussed. Updrafts occur with an average frequency of 1–2 per unit length <i>z<sub>i</sub></i> (boundary-layer depth <i>z<sub>i</sub></i>), downdrafts 20–30% more frequently. In the case with cumuli formation, the draft occurrence frequency is enhanced by about 50% at cloud level or near cloud base. The counted updraft events cover 30–34%, downdrafts 53–57% of the velocity time series in the central part of the ABL (subcloud layer) during the main period of convective activity. By considering all drafts with horizontal extent >36 m in the analysis, the updraft mean horizontal extent ranges here from 200–420 m and is about 0.16 <i>z<sub>i</sub></i>–0.18 <i>z<sub>i</sub></i> in all three cases disregarding the occurrence of cumulus clouds. Downdraft extents are a factor of 1.3–1.5 larger. The average value of the updraft mean vertical velocities is 0.5–0.7 m/s or 0.40 <i>w</i><sub>*</sub>–0.45 <i>w</i><sub>*</sub> (convective velocity scale <i>w</i><sub>*</sub>), and the negative downdraft mean vertical velocities are weaker by roughly 10–20%. The analysis of the relationship between the size (horizontal extent) of the updrafts and downdrafts and their mean vertical velocity reveals a pronounced increase of the average vertical velocity in updrafts from 0.4–0.5 m/s for small thermals (100–200 m) to about 1.5 m/s for large updrafts (>600 m) in the subcloud layer in the case with fair-weather cumuli. At cloudless conditions, the updraft velocities were found to be 20% smaller for the large thermals.
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Filter samples of fine and coarse air particulate matter (PM) collected over a period of one year in central Europe (Mainz, Germany) were analyzed for water-soluble organic compounds (WSOCs), including the α- and β-pinene oxidation products pinic acid, pinonic acid and 3-methyl-1,2,3-butanetricarboxylic acid (3-MBTCA), as well as a variety of dicarboxylic acids and nitrophenols. Seasonal variations and other characteristic features in fine, coarse, and total PM (TSP) are discussed with regard to aerosol sources and sinks in comparison to data from other studies and regions. The ratios of adipic acid and phthalic acid to azelaic acid indicate that the investigated aerosol samples were mainly influenced by biogenic sources. A strong Arrhenius-type correlation was found between the 3-MBTCA concentration and inverse temperature (<i>R</i><sup>2</sup> = 0.79, <i>n</i> = 52, <i>E</i><sub>a</sub> = 126 ± 10 kJ mol<sup>−1</sup>, temperature range 275–300 K). Model calculations suggest that the temperature dependence observed for 3-MBTCA can be explained by enhanced photochemical production due to an increase of hydroxyl radical (OH) concentration with increasing temperature, whereas the influence of gas-particle partitioning appears to play a minor role. The results indicate that the OH-initiated oxidation of pinonic acid is the rate-limiting step in the formation of 3-MBTCA, and that 3-MBTCA may be a suitable tracer for the chemical aging of biogenic secondary organic aerosol (SOA) by OH radicals. An Arrhenius-type temperature dependence was also observed for the concentration of pinic acid (<i>R</i><sup>2</sup> = 0.60, <i>n</i> = 56, <i>E</i><sub>a</sub> = 84 ± 9 kJ mol<sup>−1</sup>); it can be tentatively explained by the temperature dependence of biogenic pinene emission as the rate-limiting step of pinic acid formation.
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Atmospheric aerosol particles are able to act as cloud condensation nuclei (CCN) and are therefore important for the climate and the hydrological cycle, but their properties are not fully understood. Total CCN number concentrations at 10 different supersaturations in the range of <i>SS</i>=0.12–1.18% were measured in May 2008 at the remote high alpine research station, Jungfraujoch, Switzerland (3580 m a.s.l.). In this paper, we present a closure study between measured and predicted CCN number concentrations. CCN predictions were done using dry number size distribution (scanning particle mobility sizer, SMPS) and bulk chemical composition data (aerosol mass spectrometer, AMS, and multi-angle absorption photometer, MAAP) in a simplified Köhler theory. The predicted and the measured CCN number concentrations agree very well and are highly correlated. A sensitivity study showed that the temporal variability of the chemical composition at the Jungfraujoch can be neglected for a reliable CCN prediction, whereas it is important to know the mean chemical composition. The exact bias introduced by using a too low or too high hygroscopicity parameter for CCN prediction was further quantified and shown to be substantial for the lowest supersaturation. <br><br> Despite the high average organic mass fraction (~45%) in the fine mode, there was no indication that the surface tension was substantially reduced at the point of CCN activation. A comparison between hygroscopicity tandem differential mobility analyzer (HTDMA), AMS/MAAP, and CCN derived κ values showed that HTDMA measurements can be used to determine particle hygroscopicity required for CCN predictions if no suitable chemical composition data are available.
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Mineral dust aerosols collected during the years 2008/2009 at the high-altitude research station Jungfraujoch (46°33´, 7°59´; 3580 m a.s.l.) were compared to windblown mineral dust deposited at the Colle Gnifetti glacier (45°55´ N, 7°52´ E; 4455 m a.s.l.) over the last millennium. Insoluble dust has been characterized in terms of mineralogy, Sr and Nd isotopic ratios, and trace element composition. Results demonstrate that the Saharan origin of the airborne dust did not change significantly throughout the past. Backward trajectories analysis of modern analogs furthermore confirms that major dust sources are situated in the north-central to north-western part of the Saharan desert. By contrast, less radiogenic Sr isotopic compositions are associated with lower abundances of crustal elements during low rates of dust deposition, suggesting intercontinental transport of background dust rather than activation of a secondary source. Saharan dust mobilization and meridional advection of air masses were relatively reduced during the second part of the Little Ice Age (ca. 1690–1870), except within the greatest Saharan dust event deposited around 1780–1790. Higher dust deposition with larger mean grain size and Saharan fingerprint began ca. 20 years after the industrial revolution of 1850, suggesting that increased mineral dust transport over the Alps during the last century was primarily due to drier winters in North Africa and stronger spring/summer North Atlantic southwesterlies, rather than to direct anthropogenic sources. Meanwhile, increasing carbonaceous particle emissions from fossil fuels combustion combined to higher lead enrichment factor during the last century, point to concomitant anthropogenic sources of particulate pollutants reaching high-altitude European glaciers.
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Ultrafine particle (UFP) number and size distributions were simultaneously measured at five urban and rural sites during the summer of 2007 in Ontario, Canada as part of the Border Air Quality and Meteorology Study (BAQS-Met 2007). Particle formation and growth events at these five sites were classified based on their strength and persistence as well as the variation in geometric mean diameter. Regional nucleation and growth events and local short-lived strong nucleation events were frequently observed at the near-border rural sites, upwind of industrial sources. Surprisingly, the particle number concentrations at one of these sites were higher than the concentrations at a downtown site in a major city, despite its high traffic density. Regional nucleation and growth events were favored during intense solar irradiance and in less polluted cooler drier air. The most distinctive regional particle nucleation and growth event during the campaign was observed simultaneously at all five sites, which were up to 350 km apart. Although the ultrafine particle concentrations and size distributions generally were spatially heterogeneous across the region, a more uniform spatial distribution of UFP across the five areas was observed during this regional nucleation event. Thus, nucleation events can cover large regions, contributing to the burden of UFP in cities and potentially to the associated health impacts on urban populations. Local short-lived nucleation events at the three near-border sites during this summer three-week campaign were associated with high SO<sub>2</sub>, which likely originated from US and Canadian industrial sources. Hence, particle formation in southwestern Ontario appears to often be related to anthropogenic gaseous emissions but biogenic emissions at times also contribute. Longer-term studies are needed to help resolve the relative contributions of anthropogenic and biogenic emissions to nucleation and growth in this region.
