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Ultrafine vehicular particle (<100 nm) number size distributions presented in the literature are mostly averages of long scan-time (~30 s or more) spectra mainly due to the non-availability of commercial instruments that can measure particle distributions in the <10 nm to 100 nm range faster than 30 s even though individual researchers have built faster (1–2.5 s) scanning instruments. With the introduction of the Engine Exhaust Particle Sizer (EEPS) in 2004, high time-resolution (1 full 32-channel spectrum per second) particle size distribution data become possible and allow atmospheric researchers to study the characteristics of ultrafine vehicular particles in rapidly and perhaps randomly varying high concentration environments such as roadside, on-road and tunnel. In this study, particle size distributions in these environments were found to vary as rapidly as one second frequently. This poses the question on the generality of using averages of long scan-time spectra for dynamic and/or mechanistic studies in rapidly and perhaps randomly varying high concentration environments. One-second EEPS data taken at roadside, on roads and in tunnels by a mobile platform are time-averaged to yield 5, 10, 30 and 120 s distributions to answer this question.
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Series of infrared extinction spectra of ice crystals were recorded in the 6000–800 cm<sup>−1</sup> wavenumber regime during expansion cooling experiments in the large aerosol and cloud chamber AIDA of Forschungszentrum Karlsruhe. Either supercooled sulphuric acid solution droplets or dry mineral dust particles were added as seed aerosols to initiate ice formation after having established ice supersaturated conditions inside the chamber. The various ice nucleation runs were conducted at temperatures between 237 and 195 K, leading to median sizes of the nucleated ice particles of 1–15 µm. The measured infrared spectra were fitted with reference spectra from <b>T</b>-matrix calculations to retrieve the number concentration as well as the number size distribution of the generated ice clouds. The precise evaluation of the time-dependent ice particle number concentrations, i.e., the rates of new ice particle formation, is of particular importance to quantitatively analyse the ice nucleation experiments in terms of nucleation rates and ice activation spectra. The ice particles were modelled as finite circular cylinders with aspect ratios ranging from 0.5 to 3.0. Benefiting from the comprehensive diagnostic tools for the characterisation of ice clouds which are available at the AIDA facility, the infrared retrieval results with regard to the ice particle number concentration could be compared to independent measurements with various optical particle counters. This provided a unique chance to quantitatively assess potential errors or solution ambiguities in the retrieval procedure which mainly originate from the difficulty to find an appropriate shape representation for the aspherical particle habits of the ice crystals. Based on these inter-comparisons, we demonstrate that there is no standard retrieval approach which can be routinely applied to all different experimental scenarios. In particular, the concept to account for the asphericity of the ice crystals, the a priori constraints which might be imposed on the unknown number size distribution of the ice crystals (like employing an analytical distribution function), and the wavenumber range which is included in the fitting algorithm should be carefully adjusted to each single retrieval problem.
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A thermodynamical model for treatment of gas/aerosol partitioning of semi volatile inorganic aerosols has been implemented in a global chemistry and aerosol transport model (Oslo CTM2). The sulphur cycle and sea salt particles have been implemented earlier in the Oslo CTM2 and the focus of this study is on nitrate partitioning to the aerosol phase and if particulate nitrate is expected to form in fine or coarse mode aerosols. Modelling of the formation of fine mode nitrate particles is complicated since it depends on other aerosol components and aerosol precursors as well as meteorological condition. The surface concentrations from the model are compared to observed surface concentrations at around 20 sites around Europe for nitrate and ammonium. The agreement for nitrate is good but the modelled values are somewhat underestimated compared to observations at high concentrations, whereas for ammonium the agreement is very good. However, we underscore that such a comparison is not of large importance for the aerosol optical depth of particulate nitrate since the vertical profile of aerosol components and their precursors are so important. Fine mode nitrate formation depends on vertical profiles of both ammonia/ammonium and sulphate. The model results show that fine mode particulate nitrate play a non-negligible role in the total aerosol composition in certain industrialized regions and therefore have a significant local radiative forcing. On a global scale the aerosol optical depth of fine mode nitrate is relatively small due to limited availability of ammonia and loss to larger sea salt particles. Inclusion of sea salt in the calculations reduces the aerosol optical depth and burden of fine mode nitrate by 25% on a global scale but with large regional variations.
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The composition of organic aerosol formed from the gas phase ozonolysis of cyclohexene has been investigated in a smog chamber experiment. Comprehensive gas chromatography with time of flight mass spectrometric detection was used to determine that dicarboxylic acids and corresponding cyclic anhydrides dominated the small gas phase reaction products found in aerosol sampled during the first hour after initial aerosol formation. Structural analysis of larger more polar molecules was performed using liquid chromatography with ion trap tandem mass spectrometry. This indicated that the majority of identified organic mass was in dimer form, built up from combinations of the most abundant small acid molecules, with frequent indication of the inclusion of adipic acid. Trimers and tetramers potentially formed via similar acid combinations were also observed in lower abundances. Tandem mass spectral data indicated dimers with either acid anhydride or ester functionalities as the linkage between monomers. High-resolution mass spectrometry identified the molecular formulae of the most abundant dimer species to be C<sub>10</sub>H<sub>16</sub>O<sub>6</sub>, C<sub>11</sub>H<sub>18</sub>O<sub>6</sub>, C<sub>10</sub>H<sub>14</sub>O<sub>8</sub> and C<sub>11</sub>H<sub>16</sub>O<sub>8</sub> and could be used in some cases to reduce uncertainty in exact chemical structure determination by tandem MS.
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The new CHEM2D-Ozone Photochemistry Parameterization (CHEM2D-OPP) for high-altitude numerical weather prediction (NWP) systems and climate models specifies the net ozone photochemical tendency and its sensitivity to changes in ozone mixing ratio, temperature and overhead ozone column based on calculations from the CHEM2D interactive middle atmospheric photochemical transport model. We evaluate CHEM2D-OPP performance using both short-term (6-day) and long-term (1-year) stratospheric ozone simulations with the prototype high-altitude NOGAPS-ALPHA forecast model. An inter-comparison of NOGAPS-ALPHA 6-day ozone hindcasts for 7 February 2005 with ozone photochemistry parameterizations currently used in operational NWP systems shows that CHEM2D-OPP yields the best overall agreement with both individual Aura Microwave Limb Sounder ozone profile measurements and independent hemispheric (10°–90° N) ozone analysis fields. A 1-year free-running NOGAPS-ALPHA simulation using CHEM2D-OPP produces a realistic seasonal cycle in zonal mean ozone throughout the stratosphere. We find that the combination of a model cold temperature bias at high latitudes in winter and a warm bias in the CHEM2D-OPP temperature climatology can degrade the performance of the linearized ozone photochemistry parameterization over seasonal time scales despite the fact that the parameterized temperature dependence is weak in these regions.
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The equilibrium inorganic aerosol model ISORROPIA was embedded in a Markov Chain Monte Carlo algorithm to develop a powerful tool to analyze aerosol data and predict gas phase concentrations where these are unavailable. The method directly incorporates measurement uncertainty, prior knowledge, and provides a formal framework to combine measurements of different quality. The method was applied to particle- and gas-phase precursor observations taken at La Merced during the Mexico City Metropolitan Area (MCMA) 2003 Field Campaign and served to discriminate between diverging gas-phase observations of ammonia and predict gas-phase concentrations of hydrochloric acid. The model reproduced observations of particle-phase ammonium, nitrate, and sulfate well. The most likely concentrations of ammonia were found to vary between 4 and 26 ppbv, while the range for nitric acid was 0.1 to 55 ppbv. During periods where the aerosol chloride observations were consistently above the detection limit, the model was able to reproduce the aerosol chloride observations well and predicted the most likely gas-phase hydrochloric acid concentration varied between 0.4 and 5 ppbv. Despite the high ammonia concentrations observed and predicted by the model, when the aerosols were assumed to be in the efflorescence branch they are predicted to be acidic (pH~3).
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A Markov Chain Monte Carlo model for integrating the observations of inorganic species with a thermodynamic equilibrium model was presented in Part I of this series. Using observations taken at three ground sites, i.e. a residential, industrial and rural site, during the MCMA-2003 campaign in Mexico City, the model is used to analyze the inorganic particle and ammonia data and to predict gas phase concentrations of nitric and hydrochloric acid. In general, the model is able to accurately predict the observed inorganic particle concentrations at all three sites. The agreement between the predicted and observed gas phase ammonia concentration is excellent. The NO<sub>z</sub> concentration calculated from the NO<sub>y</sub>, NO and NO<sub>2</sub> observations is of limited use in constraining the gas phase nitric acid concentration given the large uncertainties in this measure of nitric acid and additional reactive nitrogen species. Focusing on the acidic period of 9–11 April identified by Salcedo et al. (2006), the model accurately predicts the particle phase observations during this period with the exception of the nitrate predictions after 10:00 a.m. (Central Daylight Time, CDT) on 9 April, where the model underpredicts the observations by, on average, 20%. This period had a low planetary boundary layer, very high particle concentrations, and higher than expected nitrogen dioxide concentrations. For periods when the particle chloride observations are consistently above the detection limit, the model is able to both accurately predict the particle chloride mass concentrations and provide well-constrained HCl (g) concentrations. The availability of gas-phase ammonia observations helps constrain the predicted HCl (g) concentrations. When the particles are aqueous, the most likely concentrations of HCl (g) are in the sub-ppbv range. The most likely predicted concentration of HCl (g) was found to reach concentrations of order 10 ppbv if the particles are dry. Finally, the atmospheric relevance of HCl (g) is discussed in terms of its indicator properties for the possible influence of chlorine-mediated photochemistry in Mexico City.
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Modifications of existing clouds by the exhaust of ships are well-known but inadequately quantified impacts, which could contribute to climate change. The perturbation of a cloud layer by ship-generated aerosol changes the cloud reflectivity and is identified by long curves in satellite images, known as ship tracks. As ship tracks indicate a pollution of a very clean marine environment and also affect the radiation budget below and above the cloud, it is important to investigate their radiative and climatic effects. Satellite-data from MODIS on Terra are used to examine a scene from 10 February 2003 where ship tracks were detected close to the North American West-Coast. The cloud optical and microphysical properties are derived using a semi-analytical retrieval technique combined with a look-up-table approach. An algorithm is presented to distinguish ship-track-pixels from the unperturbed cloud pixels in the scene and from this the optical properties of the former are compared to those of the latter. Within the ship tracks a significant change in the droplet number concentration, the effective radius and the optical thickness are found compared to the unaffected cloud. The resulting cloud properties are used to calculate the radiation budget below and above the cloud. Assuming a mean solar zenith angle of 63° for the selected scene, the mean solar surface radiation below the ship track is decreased by 43.2 Wm<sup>−2</sup> and the mean reflectance at top of atmosphere (TOA) is increased by 40.8 Wm<sup>−2</sup>. For the entire analyzed scene the ship emission decreases the solar radiation at the surface by 2.1 Wm<sup>−2</sup> and increases the backscattered solar radiation at TOA by 2.0 Wm<sup>−2</sup>, whereas no significant effect on thermal radiation was detected.
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Formation of secondary organic aerosol has been observed in the gas phase ozonolysis of a series of enol ethers, among them several alkyl vinyl ethers (AVE, ROCH=CH<sub>2</sub>), such as ethyl, propyl, <i>n</i>-butyl, <i>iso</i>-butyl, <i>t</i>-butyl vinyl ether, and ethyl propenyl ether (EPE, C<sub>2</sub>H<sub>5</sub>OCH=CHCH<sub>3</sub>). The ozonolysis has been studied in a 570 l spherical glass reactor at ambient pressure (730 Torr) and room temperature (296 K). Gas phase reaction products were investigated by in-situ FTIR spectroscopy, and secondary organic aerosol (SOA) formation was monitored by a scanning mobility particle sizer (SMPS). The chemical composition of the formed SOA was analysed by a hybrid mass spectrometer using electrospray ionization (ESI). The main stable gas phase reaction product is the respective alkyl formate ROC(O)H, formed with yields of 60 to 80%, implying that similar yields of the corresponding excited Criegee Intermediates (CI) CH<sub>2</sub>O<sub>2</sub> for the AVE and CH<sub>3</sub>CHO<sub>2</sub> for EPE are generated. Measured SOA yields are between 2 to 4% for all enol ethers. Furthermore, SOA formation is strongly reduced or suppressed by the presence of an excess of formic acid, which acts as an efficient CI scavenger. <br><br> Chemical analysis of the formed SOA by ESI(+)/MS-TOF allows to identify oligomeric compounds in the mass range 200 to 800 u as its major constituents. Repetitive chain units are identified as CH<sub>2</sub>O<sub>2</sub> (mass 46) for the AVE and C<sub>2</sub>H<sub>4</sub>O<sub>2</sub> (mass 60) for EPE and thus have the same chemical compositions as the respective major Criegee Intermediates formed during ozonolysis of these ethers. The oligomeric structure and chain unit identity are confirmed by HPLC/ESI(+)/MS-TOF and ESI(+)/MS/MS-TOF experiments, whereby successive and systematic loss of a fragment with mass 46 for the AVE (and mass 60 for EPE) is observed. It is proposed that the oligomer has the following basic structure of an oligoperoxide, -[CH(R)-O-O]<sub>n</sub>-, where R=H for the AVE and R=CH<sub>3</sub> for the EPE. Oligoperoxide formation is thus suggested to be another, so far unknown reaction of stabilized Criegee Intermediates in the gas phase ozonolysis of oxygen-containing alkenes leading to SOA formation.
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Trends in ozone columns and vertical distributions were calculated for the period 1979–2004 based on the ozone data set CATO (Candidoz Assimilated Three-dimensional Ozone) using a multiple linear regression model. CATO has been reconstructed from TOMS, GOME and SBUV total column ozone observations in an equivalent latitude and potential temperature framework and offers a pole to pole coverage of the stratosphere on 15 potential temperature levels. The regression model includes explanatory variables describing the influence of the quasi-biennial oscillation (QBO), volcanic eruptions, the solar cycle, the Brewer-Dobson circulation, Arctic ozone depletion, and the increase in stratospheric chlorine. The effects of displacements of the polar vortex and jet streams due to planetary waves, which may significantly affect trends at a given geographical latitude, are eliminated in the equivalent latitude framework. The QBO shows a strong signal throughout most of the lower stratosphere with peak amplitudes in the tropics of the order of 10–20% (peak to valley). The eruption of Pinatubo led to annual mean ozone reductions of 15–25% between the tropopause and 23 km in northern mid-latitudes and to similar percentage changes in the southern hemisphere but concentrated at altitudes below 17 km. Stratospheric ozone is elevated over a broad latitude range by up to 5% during solar maximum compared to solar minimum, the largest increase being observed around 30 km. This is at a lower altitude than reported previously, and no negative signal is found in the tropical lower stratosphere. The Brewer-Dobson circulation shows a dominant contribution to interannual variability at both high and low latitudes and accounts for some of the ozone increase seen in the northern hemisphere since the mid-1990s. Arctic ozone depletion significantly affects the high northern latitudes between January and March and extends its influence to the mid-latitudes during later months. The vertical distribution of the ozone trend shows distinct negative trends at about 18 km in the lower stratosphere with largest declines over the poles, and above 35 km in the upper stratosphere. A narrow band of large negative trends extends into the tropical lower stratosphere. Assuming that the observed negative trend before 1995 continued to 2004 cannot explain the ozone changes since 1996. A model accounting for recent changes in equivalent effective stratospheric chlorine, aerosols and Eliassen-Palm flux, on the other hand, closely tracks ozone changes since 1995.
