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Of all satellite measurements of ozone, only two instruments have coincident, spatially overlapping measurements to allow direct comparison of tropospheric column ozone (TCO): the Ozone Monitoring Instrument (OMI) and the Tropospheric Emission Spectrometer (TES) on the NASA Aura spacecraft. For two years (2005–2006), we collect all observations between 60° S and 60° N from nadir (~65 000 from OMI and TES) and cross-track swaths (~30 000 000 from OMI) and compare with a chemistry-transport model (CTM) simulating each observation with corresponding spatial and temporal coincidence. High-frequency TCO variations are indicative of stratospheric intrusions of ozone-rich air, and the individual, level 2 data provide access to these short-lived phenomena. Although we can identify some seasonal and large-scale biases in the model, the CTM as a transfer standard identifies weaknesses in the observations and further helps quantify the measurement noise of individual profiles. The relatively noise-free CTM bridges these two satellite measurements and improves their cross-validation to better precision than a simple direct comparison. Previous validation studies of TES TCO versus ozonesondes found a bias of about +4 Dobson Units (DU) for large regions. The three-way comparison and the CTM transfer method that use a far greater number of coincidences, indicate that monthly zonal mean OMI-TES TCO biases fall within 5–10%, and thus quantifies the zonal mean OMI TCO bias at a few DU. For small regions (i.e., 5 × 5°), however, the monthly mean OMI-TES differences can exceed ±10 DU at many places (e.g., tropics for the direct OMI-TES comparison) due to different tropospheric sensitivities of the two instruments at these locations. Partly removing the influence of different sensitivities by applying the CTM as the transfer standard, the OMI-TES differences generally decrease, especially over the tropics. In addition, the CTM-TES comparison split into day versus night observations shows no apparent bias in TES at very low levels, ±1 DU. These OMI-TES-CTM comparisons highlight the importance of the a priori ozone profiles that went into each satellite retrieval, including a false agreement due to CTM-a priori similarity, and the importance of including the vertical information (i.e., averaging kernel) in the retrieval products. This study also highlights the advantages of overlapping measurements in terms of cross-validation and the application of a model as the transfer standard.
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The impact of climate change on surface ozone over Europe was studied using four offline regional chemistry transport models (CTMs) and one online regional integrated climate-chemistry model (CCM), driven by the same global projection of future climate under the SRES A1B scenario. Anthropogenic emissions of ozone precursors from RCP4.5 for year 2000 were used for simulations of both present and future periods in order to isolate the impact of climate change and to assess the robustness of the results across the different models. The sensitivity of the simulated surface ozone to changes in climate between the periods 2000–2009 and 2040–2049 differs by a factor of two between the models, but the general pattern of change with an increase in southern Europe is similar across different models. Emissions of isoprene differ substantially between different CTMs ranging from 1.6 to 8.0 Tg yr<sup>−1</sup> for the current climate, partly due to differences in horizontal resolution of meteorological input data. Also the simulated change in total isoprene emissions varies substantially across models explaining part of the different climate response on surface ozone. Ensemble mean changes in summer mean ozone and mean of daily maximum ozone are close to 1 ppb(v) in parts of the land area in southern Europe. Corresponding changes of 95-percentiles of hourly ozone are close to 2 ppb(v) in the same region. In northern Europe ensemble mean for mean and daily maximum show negative changes while there are no negative changes for the higher percentiles indicating that climate impacts on O<sub>3</sub> could be especially important in connection with extreme summer events.
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Amino acids are significant components of atmospheric aerosols, affecting organic nitrogen input to marine ecosystems, atmospheric radiation balance, and the global water cycle. The wide range of amino acid reactivities suggest that amino acids may serve as markers of atmospheric transport and deposition of particles. Despite this potential, few measurements have been conducted in remote areas to assess amino acid concentrations and potential sources. Polar regions offer a unique opportunity to investigate atmospheric processes and to conduct source apportionment studies of such compounds. In order to better understand the importance of amino acid compounds in the global atmosphere, we determined free amino acids (FAAs) in seventeen size-segregated aerosol samples collected in a polar station in the Svalbard Islands from 19 April until 14 September 2010. We used an HPLC coupled with a tandem mass spectrometer (ESI-MS/MS) to analyze 20 amino acids and quantify compounds at fmol m<sup>−3</sup> levels. Mean total FAA concentration was 1070 fmol m<sup>−3</sup> where serine and glycine were the most abundant compounds in almost all samples and accounted for 45–60% of the total amino acid relative abundance. The other eighteen compounds had average concentrations between 0.3 and 98 fmol m<sup>−3</sup>. The higher amino acid concentrations were present in the ultrafine aerosol fraction (< 0.49 μm) and accounted for the majority of the total amino acid content. Local marine sources dominate the boreal summer amino acid concentrations, with the exception of the regional input from Icelandic volcanic emissions.
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The article presents the laser scattering and depolarisation instrument SIMONE that is installed at the large aerosol and cloud chamber facility AIDA of the Karlsruhe Institute of Technology. SIMONE uses a 488 nm cw laser to probe simulated atmospheric clouds by measuring the scattered light from the 1.8° and 178.2° directions. At 178.2°, the scattered light is analysed for the linear polarisation state to deduce the particle linear depolarisation ratio δ<sub>p</sub> which is a common measurement parameter of atmospheric lidar applications. The optical setup and the mathematical formalism of the depolarisation detection concept are given. SIMONE depolarisation measurements in spheroidal hematite aerosol and supercooled liquid clouds are used to validate the instrument. <br><br> SIMONE data from a series of AIDA ice nucleation experiments at temperatures between 195 and 225 K were analysed in terms of the impact of the ice particle microphysics on δ<sub>p</sub>. We found strong depolarisation values of up to 0.4 in case of small growing and sublimating ice particles with volume equivalent diameters of only a few micrometers. <br><br> Modelling runs with the T-matrix method showed that the measured depolarisation ratios can be accurately reproduced assuming spheroidal and cylindrical particles with a size distribution that has been constrained by IR extinction spectroscopy. Based on the T-matrix modelling runs, we demonstrate that in case of small ice crystals the SIMONE depolarisation results are representative for the lidar depolarisation ratio which is measured at exact backscattering direction of 180°. <br><br> The relevance of our results for the interpretation of recent lidar observations in cirrus and contrails is discussed. In view of our results, the high depolarisation ratios observed by the spaceborne lidar CALIOP in the tropical upper troposphere might be a hint for the presence of small (sublimating) ice particles in the outflows of deep convective systems.
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Actinic flux, as well as aerosol chemical and optical properties, were measured aboard the NASA DC-8 aircraft during the ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) mission in Spring and Summer 2008. These measurements were used in a radiative transfer code to retrieve spectral (350–550 nm) aerosol single scattering albedo (SSA) for biomass burning plumes encountered on 17 April and 29 June. Retrieved SSA values were subsequently used to calculate the absorption Angstrom exponent (AAE) over the 350–500 nm range. Both plumes exhibited enhanced spectral absorption with AAE values that exceeded 1 (6.78 ± 0.38 for 17 April and 3.34 ± 0.11 for 29 June). This enhanced absorption was primarily due to organic aerosol (OA) which contributed significantly to total absorption at all wavelengths for both 17 April (57.7%) and 29 June (56.2%). OA contributions to absorption were greater at UV wavelengths than at visible wavelengths for both cases. Differences in AAE values between the two cases were attributed to differences in plume age and thus to differences in the ratio of OA and black carbon (BC) concentrations. However, notable differences between AAE values calculated for the OA (AAE<sub>OA</sub>) for 17 April (11.15 ± 0.59) and 29 June (4.94 ± 0.19) suggested differences in the plume AAE values might also be due to differences in organic aerosol composition. The 17 April OA was much more oxidized than the 29 June OA as denoted by a higher oxidation state value for 17 April (+0.16 vs. −0.32). Differences in the AAE<sub>OA</sub>, as well as the overall AAE, were thus also possibly due to oxidation of biomass burning primary organic aerosol in the 17 April plume that resulted in the formation of OA with a greater spectral-dependence of absorption.
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Retrievals of the isotopic composition of water vapor from the Aura Tropospheric Emission Spectrometer (TES) have unique value in constraining moist processes in climate models. Accurate comparison between simulated and retrieved values requires that model profiles that would be poorly retrieved are excluded, and that an instrument operator be applied to the remaining profiles. Typically, this is done by sampling model output at satellite measurement points and using the quality flags and averaging kernels from individual retrievals at specific places and times. This approach is not reliable when the model meteorological conditions influencing retrieval sensitivity are different from those observed by the instrument at short time scales, which will be the case for free-running climate simulations. In this study, we describe an alternative, "categorical" approach to applying the instrument operator, implemented within the NASA GISS ModelE general circulation model. Retrieval quality and averaging kernel structure are predicted empirically from model conditions, rather than obtained from collocated satellite observations. This approach can be used for arbitrary model configurations, and requires no agreement between satellite-retrieved and model meteorology at short time scales. To test this approach, nudged simulations were conducted using both the retrieval-based and categorical operators. Cloud cover, surface temperature and free-tropospheric moisture content were the most important predictors of retrieval quality and averaging kernel structure. There was good agreement between the δD fields after applying the retrieval-based and more detailed categorical operators, with increases of up to 30‰ over the ocean and decreases of up to 40‰ over land relative to the raw model fields. The categorical operator performed better over the ocean than over land, and requires further refinement for use outside of the tropics. After applying the TES operator, ModelE had δD biases of −8‰ over ocean and −34‰ over land compared to TES δD, which were less than the biases using raw model δD fields.
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The present study investigates the dust emission and load over the Mediterranean basin using the coupled chemistry–aerosol–regional climate model RegCM-4. The first step of this work focuses on dust particle emission size distribution modeling. We compare a parameterization in which the emission is based on the individual kinetic energy of the aggregates striking the surface to a recent parameterization based on an analogy with the fragmentation of brittle materials. The main difference between the two dust schemes concerns the mass proportion of fine aerosol that is reduced in the case of the new dust parameterization, with consequences for optical properties. At the episodic scale, comparisons between RegCM-4 simulations, satellite and ground-based data show a clear improvement using the new dust distribution in terms of aerosol optical depth (AOD) values and geographic gradients. These results are confirmed at the seasonal scale for the investigated year 2008. This change of dust distribution has sensitive impacts on the simulated regional dust budget, notably dry dust deposition and the regional direct aerosol radiative forcing over the Mediterranean basin. In particular, we find that the new size distribution produces a higher dust deposition flux, and smaller top of atmosphere (TOA) dust radiative cooling. A multi-annual simulation is finally carried out using the new dust distribution over the period 2000–2009. The average SW radiative forcing over the Mediterranean Sea reaches −13.6 W m<sup>−2</sup> at the surface, and −5.5 W m<sup>−2</sup> at TOA. The LW radiative forcing is positive over the basin: 1.7 W m<sup>−2</sup> on average over the Mediterranean Sea at the surface, and 0.6 W m<sup>−2</sup> at TOA.
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An improved Gas and Aerosol Collector (GAC) equipped with a newly designed aerosol collector and a set of dull-polished wet annular denuder (WAD) was developed based on a Steam Jet Aerosol Collector (SJAC) sampler. Combined with Ion Chromatography (IC) the new sampler performed well in laboratory tests with high collection efficiencies for SO<sub>2</sub> (above 98%) and particulate sulfate (as high as 99.5%). An inter-comparison between the GAC-IC system and the filter-pack method was performed and the results indicated that the GAC-IC system could supply reliable particulate sulfate, nitrate, chloride, and ammonium data in field measurement with a much wider range of ambient concentrations. When applied in two major field campaigns (rural and coastal sites) in China, the GAC-IC system provided high-quality data in ambient conditions even under high loadings of pollutants. Its measurements were highly correlated with data by other commercial instruments such as the SO<sub>2</sub> analyzer (43c, Thermo-Fisher, USA; <i>R</i><sup>2</sup> as 0.96), the HONO analyzer (LOPAP, Germany; <i>R</i><sup>2</sup> as 0.91 for samples from 15:00 to 07:00), a filter sampler (Tianhong, China; <i>R</i><sup>2</sup> as 0.86 for SO<sub>4</sub><sup>2−</sup>), and Aerosol Mass Spectrometer (AMS, Aerodyne, USA; <i>R</i><sup>2</sup> above 0.77 for major species) over a wide range of concentrations. Through the application of the GAC-IC system, it was identified that 70% of chloride and nitrate by the filter method could be lost during daytime sampling due to high temperature in the rural site of Kaiping. In Changdao field campaign (coastal site), though a particle dryer was applied, its drying efficiency was not well considered for the collection efficiency of AMS seemed still interfered a bit by local high relative humidity. If the inter-comparison was done with relative humidity below 50%, the correlations ranged from 0.81 to 0.94 for major species. Through laboratory and field studies, this instrument is proved particularly useful in future intensive campaigns or long-term monitoring stations to study various environmental issues such as secondary aerosol and haze formation, as well as climate change.
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This work presents a simulation of the plume trajectory emitted by flaring activities of the Miguel Hidalgo Refinery in Mexico. The flame of a representative sour gas flare is modeled with a CFD combustion code in order to estimate emission rates of combustion by-products of interest for air quality: acetylene, ethylene, nitrogen oxides, carbon monoxide, soot and sulfur dioxide. The emission rates of NO<sub>2</sub> and SO<sub>2</sub> were compared with measurements obtained at Tula as part of MILAGRO field campaign. The rates of soot, VOCs and CO emissions were compared with estimates obtained by Instituto Mexicano del Petróleo (IMP). The emission rates of these species were further included in WRF-Chem model to simulate the chemical transport of the plume from 22 to 27 March of 2006. The model presents reliable performance of the resolved meteorology, with respect to the Mean Absolute Error (MAE), Root Mean Square Error (RMSE), mean bias (BIAS), vector RMSE and Index of Agreement (IOA). <br><br> WRF-Chem outputs of SO<sub>2</sub> and soot were compared with surface measurements obtained at the three supersites of MILAGRO campaign. The results suggest a contribution of Tula flaring activities to the total SO<sub>2</sub> levels of 18% to 27% at the urban supersite (T0), and of 10% to 18% at the suburban supersite (T1). For soot, the model predicts low contribution at the three supersites, with less than 0.1% at three supersites. According to the model, the greatest contribution of both pollutants to the three supersites occurred on 23 March, which coincides with the third cold surge event reported during the campaign.
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Understanding the transport path of the solar activity proxy <sup>10</sup>Be from source to archive is crucial for the interpretation of its observed variability. The extent of mixing of the strong production signal has been quantified in a previous study (Heikkilä et al., 2009). In this study we perform sensitivity studies to investigate the influence of model resolution on the degree of mixing and transport path of <sup>10</sup>Be in the atmosphere using the ECHAM5-HAM aerosol-climate model. This study permits us to choose an acceptable resolution, and so minimum CPU time, to produce reconstructions as physically accurate as possible. Five model resolutions are applied: T21L19: a coarse horizontal and vertical resolution with model top at ca. 30 km, T42L31: an average horizontal and fine vertical one, T42L39: similar vertical resolution than L19 but including the middle atmosphere up to ca. 80 km, T63L31: a fine horizontal and vertical resolution and T63L47: a fine resolution horizontally and vertically with middle atmosphere. Comparison with observations suggests that a finer horizontal and vertical resolution might be beneficial, producing a reduced meridional gradient, although the spread between observations was much larger than between the five model runs. In terms of atmospheric mixing the differences became more distinguishable. All resolutions agreed that the main driver of deposition variability, observed in natural archives, is the input of stratospheric <sup>10</sup>Be (total contribution 68%) which is transported into the troposphere at latitudes 30–50°. In the troposphere the model resolutions deviated largely in the dispersion of the stratospheric component over latitude. The finest resolution (T63L47) predicted the least dispersion towards low latitudes but the most towards the poles, whereas the coarsest resolution (T21L19) suggested the opposite. The tropospheric components of <sup>10</sup>Be differed less between the five model runs. The largest differences were found in the polar tropospheric components, which contribute the least to total production (≈ 4%). We conclude that the use of the T42 horizontal resolution seems to be sufficient in terms of atmospheric mixing of a stratospheric tracer because no substantial improvement was seen when the resolution was increased from T42 to T63. The use of the middle atmospheric configuration is a trade-off between correctly describing stratospheric dynamics and having to reduce vertical resolution. The use of a high vertical resolution seemed more beneficial than the middle atmospheric configuration in this study. The differences found between the T42L31 and T63L31 resolutions were so small that T42L31 is a good choice because of its computational efficiency.
