Probing ice clouds by broadband mid-infrared extinction spectroscopy: case studies from ice nucleation experiments in the AIDA aerosol and cloud chamber

International audienceSeries of infrared extinction spectra of ice crystals were recorded in the 6000?800 cm-1 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 T-matrix calculations to retrieve the number concentration as well as the number size distribution of the generated ice clouds. 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

Technical Note: A numerical test-bed for detailed ice nucleation studies in the AIDA cloud simulation chamber

The AIDA (Aerosol Interactions and Dynamics in the Atmosphere) aerosol and cloud chamber of Forschungszentrum Karlsruhe can be used to test the ice forming ability of aerosols. The AIDA chamber is extensively instrumented including pressure, temperature and humidity sensors, and optical particle counters. Expansion cooling using mechanical pumps leads to ice supersaturation conditions and possible ice formation. In order to describe the evolving chamber conditions during an expansion, a parcel model was modified to account for diabatic heat and moisture interactions with the chamber walls. Model results are shown for a series of expansions where the initial chamber temperature ranged from &minus;20&deg;C to &minus;60&deg;C and which used desert dust as ice forming nuclei. During each expansion, the initial formation of ice particles was clearly observed. For the colder expansions there were two clear ice nucleation episodes. <br><br> In order to test the ability of the model to represent the changing chamber conditions and to give confidence in the observations of chamber temperature and humidity, and ice particle concentration and mean size, ice particles were simply added as a function of time so as to reproduce the observations of ice crystal concentration. The time interval and chamber conditions over which ice nucleation occurs is therefore accurately known, and enables the model to be used as a test bed for different representations of ice formation

Constraining a hybrid volatility basis-set model for aging of wood-burning emissions using smog chamber experiments : A box-model study based on the VBS scheme of the CAMx model (v5.40)

In this study, novel wood combustion aging experiments performed at different temperatures (263 and 288 K) in a ∼ 7 m³ smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol–chemistry box-model simulations with unprecedented measurements of non-traditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). Due to this, we are able to observationally constrain the amounts of different NTVOC aerosol precursors (in the model) relative to low volatility and semi-volatile primary organic material (OM$_{sv}$), which is partitioned based on current published volatility distribution data. By comparing the NTVOC ∕ OM$_{sv}$ ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass-burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30 000 box-model simulations were performed to retrieve the combination of parameters that best fit the observed organic aerosol mass and O : C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O : C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ∼ 4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 h of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10$^{-11}$ to 4. 0 × 10$^{-11}$ cm³ molec$^{-1}$ s$^{-1}$. The average enthalpy of vaporization of secondary organic aerosol (SOA) surrogates was determined to be between 55 000 and 35 000 J mol$^{-1}$, which implies a yield increase of 0.03-0.06 % K$^{-1}$ with decreasing temperature. The improved VBS scheme is suitable for implementation into chemical transport models to predict the burden and oxidation state of primary and secondary biomass-burning aerosols

Numerical simulations of homogeneous freezing processes in the aerosol chamber AIDA

The homogeneous freezing of supercooled H₂SO₄/H₂O aerosols in an aerosol chamber is investigated with a microphysical box model using the activity parameterization of the nucleation rate by Koop et al. (2000). The simulations are constrained by measurements of pressure, temperature, total water mixing ratio, and the initial aerosol size distribution, described in a companion paper Möhler et al. (2003). Model results are compared to measurements conducted in the temperature range between 194 and 235 K, with cooling rates in the range between 0.5 and 2.6 K min^-1, and at air pressures between 170 and 1000 hPa. The simulations focus on the time history of relative humidity with respect to ice, aerosol size distribution, partitioning of water between gas and particle phase, onset times of freezing, freezing threshold relative humidities, aerosol chemical composition at the onset of freezing, and the number of nucleated ice crystals. The latter four parameters can be inferred from the experiments, the former three aid in interpreting the measurements. Sensitivity studies are carried out to address the relative importance of uncertainties of basic quantities such as temperature, total H₂O mixing ratio, aerosol size spectrum, and deposition coefficient of H₂O molecules on ice. The ability of the numerical simulations to provide detailed explanations of the observations greatly increases confidence in attempts to model this process under real atmospheric conditions, for instance with regard to the formation of cirrus clouds or polar stratospheric ice clouds, provided that accurate temperature and humidity measurements are available

Heterogeneous ice nucleation activity of bacteria: new laboratory experiments at simulated cloud conditions

The ice nucleation activities of five different &lt;i&gt;Pseudomonas syringae&lt;/i&gt;, &lt;i&gt;Pseudomonas viridiflava&lt;/i&gt; and &lt;i&gt;Erwinia herbicola&lt;/i&gt; bacterial species and of Snomax™ were investigated in the temperature range between &amp;minus;5 and &amp;minus;15&amp;deg;C. Water suspensions of these bacteria were directly sprayed into the cloud chamber of the AIDA facility of Forschungszentrum Karlsruhe at a temperature of &amp;minus;5.7&amp;deg;C. At this temperature, about 1% of the Snomax™ cells induced immersion freezing of the spray droplets before the droplets evaporated in the cloud chamber. The living cells didn&apos;t induce any detectable immersion freezing in the spray droplets at &amp;minus;5.7&amp;deg;C. After evaporation of the spray droplets the bacterial cells remained as aerosol particles in the cloud chamber and were exposed to typical cloud formation conditions in experiments with expansion cooling to about &amp;minus;11&amp;deg;C. During these experiments, the bacterial cells first acted as cloud condensation nuclei to form cloud droplets. Then, only a minor fraction of the cells acted as heterogeneous ice nuclei either in the condensation or the immersion mode. The results indicate that the bacteria investigated in the present study are mainly ice active in the temperature range between &amp;minus;7 and &amp;minus;11&amp;deg;C with an ice nucleation (IN) active fraction of the order of 10&lt;sup&gt;&amp;minus;4&lt;/sup&gt;. In agreement to previous literature results, the ice nucleation efficiency of Snomax™ cells was much larger with an IN active fraction of 0.2 at temperatures around &amp;minus;8&amp;deg;C

Na-O Anticorrelation and HB. VI. The chemical composition of the peculiar bulge globular cluster NGC 6388

We present the LTE abundance analysis of high resolution spectra for red giant stars in the peculiar bulge globular cluster NGC 6388. Spectra of seven members were taken using the UVES spectrograph at the ESO VLT2 and the multiobject FLAMES facility. We exclude any intrinsic metallicity spread in this cluster: on average, [Fe/H]=-0.44+/-0.01+/-0.03 dex on the scale of the present series of papers, where the first error bar refers to individual star-to-star errors and the second is systematic, relative to the cluster. Elements involved in H-burning at high temperatures show large spreads, exceeding the estimated errors in the analysis. In particular, the pairs Na and O, Al and Mg are anticorrelated and Na and Al are correlated among the giants in NGC 6388, the typical pattern observed in all galactic globular clusters studied so far. Stars in NGC 6388 shows an excess of alpha-process elements, similar to the one found in the twin bulge cluster NGC 6441. Mn is found underabundant in NGC 6388, in agreement with the average abundance ratio shown by clusters of any metallicity. Abundances of neutron-capture elements are homogeneously distributed within NGC 6388; the [Eu/Fe] ratio stands above the value found in field stars of similar metallicity