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Modelling the cloud condensation nucleus activity of organic acids on the basis of surface tension and osmolality measurements

In this study vapour pressure osmometry was used to determine water activity in the solutions of organic acids. The surface tension of the solutions was also monitored in parallel and then Köhler curves were calculated for nine organic acids (oxalic, malonic, succinic, glutaric, adipic, maleic, malic, citric and cis-pinonic). Surface tension depression is negligible for most of the organic acids in dilute (≤1 w/w%) solutions. Therefore, these compounds affect equilibrium vapour pressure only in the beginning phase of droplet formation when the droplet solution is more concentrated but not necessarily at the critical size. An exception is cis-pinonic acid which remarkably depress surface tension also in dilute (0.1 w/w%) solution and hence at the critical point. The surface tension of organic acid solutions is influenced by the solubility of the compound, the length of the carbon chain and also by the polar functional groups present in the molecule. Similarly to surface tension solubility plays an important role also in water activity: compounds with higher solubility (e.g. malonic, maleic and glutaric acid) reduce water activity significantly in the early phase of droplet formation while less soluble acids (e.g. succinic and adipic acid) are saturated in small droplets and the solution starts diluting only in bigger droplets. As a consequence, compounds with lower solubility have a minor effect on water activity in the early phase of droplet formation. To deduce the total effect Köhler curves were calculated and critical supersaturations (Sc) were determined for the organic acids using measured surface tension and water activity. It was found that critical supersaturation grew with growing carbon number. Oxalic acid had the lowest critical supersaturation in the size range studied and it was comparable to the activation of ammonium sulphate. The Sc values obtained in this study were compared to data from CCNC experiments. In most cases good agreement was found. For modelling purposes Sc vs. ddry plots are given and the dependence of water activity and surface tension on concentration are also formulated.
Cospectral analysis of high frequency signal loss in eddy covariance measurements

The cospectra of momentum (M), sensible heat (H), latent heat (LE), and carbon dioxide (Fc) fluxes measured by eddy covariance (EC) over a shortgrass steppe are calculated for over 800 time intervals spanning a range of wind, surface heating, evaporative, and photosynthetic conditions. The power spectrum of the vertical wind clearly shows that the inertial subrange is not sufficiently captured. The cospectra of the different fluxes show that the lack of measurement resolution in the high frequency results in a loss of flux, especially as stability approaches neutral. A procedure is outlined to use statistics from the cospectrum to estimate the amount of high-frequency flux that remains unmeasured for each time interval. The greatest loss of flux was for H (14% on average for 0>z/L>0.001 where z/L is the dimensionless stability), consistent with other studies which indicate temperature fluctuations actively produce turbulence at high frequencies. LE and Fc showed less than half as much loss of flux as H. This differential loss of flux has direct implications for addressing energy balance closure in EC studies, as well as reconciling biases of fluxes measured by EC with the Modified Bowen Ratio technique. It is recommended that the cospectra of fluxes be examined while setting the height of instrumentation in order to insure that high frequency eddies are resolved.
Properties of polar stratospheric clouds obtained by combined ACE-FTS and ACE-Imager extinction measurements

We report the compositions and size distributions of aerosol particles in typical polar stratospheric clouds (PSCs) observed between 24 January and 28 February 2005 in the Arctic stratosphere. The results are obtained by combining the extinction measurements made by the Atmospheric Chemistry Experiment (ACE) Fourier-Transform Spectrometer and the visible/near IR imagers on the SCISAT satellite. The extended wavenumber range provided by this combination (750 to 20 000 cm−1) enables the retrieval of aerosol particle sizes between 0.05 and 10 μm as well as providing extensive information about the compositions. Our results indicate that liquid ternary solutions with a high (>30 wt%) content of HNO3 were the most probable component of the clouds at the (60–70° N) latitudes accessible by ACE. The mean size of these ternary aerosol particles is in the range of 0.3 to 0.8 μm. Less abundant, although still frequent, were clouds composed of NAT particles having radii in the range of 1 μm and clouds of ice particles having mean radii in the 4–5 μm range. In some cases, these last two types were found in the same observation.
On the contribution of Aitken mode particles to cloud droplet populations at continental background areas – a parametric sensitivity study

Aitken mode particles are potentially an important source of cloud droplets in continental background areas. In order to find out which physico-chemical properties of Aitken mode particles are most important regarding their cloud-nucleating ability, we calculated the number of cloud droplets formed on Aitken mode particles, CD2, with an adiabatic air parcel model. The model output was analyzed using a global sensitivity analysis method that quantifies and ranks the relative importance of the considered input parameters to the total variance of CD2. The results show that unless the particle surface tension or the mass accommodation coefficient of water is strongly reduced due to the presence of surface-active organics, the parameters describing the size distribution are generally more important than the particle chemical composition. In the absence of such compounds, the chemical composition may have roughly an equal importance with the size distribution only at low updraft velocities characterized by maximum supersaturations below 0.1%. Furthermore, the largest source of variability is generally the particle number concentration, followed by the particle size. The performed sensitivity analysis revealed that the variability of the particle chemical composition may dominate the total variation of CD2 if: 1) the value of α varies at least one order of magnitude more than what is expected for pure water surfaces (10−2–1), or 2) the particle surface tension varies more than roughly 30% under conditions close to reaching saturation.
ISORROPIA II: a computationally efficient thermodynamic equilibrium model for K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosols

This study presents ISORROPIA II, a thermodynamic equilibrium model for the K+–Ca2+–Mg2+–NH4+–Na+–SO42−–NO3−–Cl−–H2O aerosol system. A comprehensive evaluation of its performance is conducted against water uptake measurements for laboratory aerosol and predictions of the SCAPE2 thermodynamic module over a wide range of atmospherically relevant conditions. The two models agree well, to within 13% for aerosol water content and total PM mass, 16% for aerosol nitrate and 6% for aerosol chloride and ammonium. Largest discrepancies were found under conditions of low RH, primarily from differences in the treatment of water uptake and solid state composition. In terms of computational speed, ISORROPIA II was more than an order of magnitude faster than SCAPE2, with robust and rapid convergence under all conditions. The addition of crustal species does not slow down the thermodynamic calculations (compared to the older ISORROPIA code) because of optimizations in the activity coefficient calculation algorithm. Based on its computational rigor and performance, ISORROPIA II appears to be a highly attractive alternative for use in large scale air quality and atmospheric transport models.
The influence of cloud top variability from radar measurements on 3-D radiative transfer

In radiative transfer simulations the simplification of cloud top structure by homogeneous assumptions can cause mistakes in comparison to realistic heterogeneous cloud top structures. This paper examines the influence of cloud top heterogeneity on the radiation at the top of the atmosphere. The use of cloud top measurements with a high temporal resolution allows the analysis of small spatial cloud top heterogeneities by using the frozen turbulence assumption for the time – space conversion. Radiative observations are often based on satellite measurements, whereas small spatial structures are not considered in such treatments. A spectral analysis of the cloud top measurements showed slopes of power spectra between –1.8 and –2.0, these values are larger than the spectra of –5/3 which is often applied to generate cloud field variability. The comparison of 3-D radiative transfer results from cloud fields with homogeneous and heterogeneous tops has been done for a single wavelength of 0.6 μm. The radiative transfer calculations result in lower albedos for heterogeneous cloud tops. The differences of albedos between heterogeneous and homogeneous cloud top decrease with increasing solar zenith angle. The influence of cloud top variability on radiances is shown. The reflectances for heterogeneous tops are explicitly larger in forward direction, in backward direction lower. The largest difference of the mean reflectances (mean over cloud field) between homogeneous and heterogeneous cloud top is approximately 0.3, which is 30% of illumination.
A new atmospheric aerosol phase equilibrium model (UHAERO): organic systems

In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c) to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored.
Tropospheric OH and Cl levels deduced from non-methane hydrocarbon measurements in a marine site

In situ continuous hourly measurements of C2–C8 non-methane hydrocarbons (NMHCS) have been performed from March to October 2006 at two coastal locations (natural and rural) on the island of Crete, in the Eastern Mediterranean. Well defined diel variations were observed for several short lived NMHCS (including ethene, propene, n-butane, n-pentane, n-hexane, 2-methyl-pentane). The daytime concentration of hydroxyl (OH) radicals estimated from these experimental data varied from 1.3×106 to ~4.0×106 radical cm−3, in good agreement with box-model simulations. In addition the relative variability of various hydrocarbon pairs (at least 7) was used to derive the tropospheric levels of Cl atoms. The Cl atom concentration has been estimated to range between 0.6×104 and 4.7×104 atom cm−3, in good agreement with gaseous hydrochloric acid (HCl) observations in the area. Such levels of Cl atoms can be of considerable importance for the oxidation capacity of the troposphere on a regional scale.
Non-methane hydrocarbons source apportionment at different sites in Mexico City during 2002–2003

The atmospheric concentrations of a variety of non-methane hydrocarbons (NMHC) collected at different sites, representing urban and rural environments within Mexico City Metropolitan Area (MCMA) during 1997, 2002 and 2003 field campaigns, were compared and used as an input for the Chemical Mass Balance (CMB) receptor model to determine the source contribution of NMHC to the atmosphere. A common feature at all the locations was the dominance of alkenes (59%), aromatics (16%) and olefins (9%) in the average NMHC burden. At the urban sites the interquartile range of NMHC concentrations showed stabilization over this period with a slight increase in the concentrations of propane and butanes in the southwest site of the MCMA in 2003 due to the increased use of liquefied petroleum gas (LPG). The receptor model CMB version 8.0 was used to apportion the NMHC sources at six locations within the MCMA, representing the heavily industrialized, commercial, residential and rural areas. For the 2003 field campaign, the contribution of vehicular emissions dominated the NMHC concentrations (19.7%±7.1% for gasoline vehicles and 35.4%±17.5% for diesel vehicles) followed by the emissions of marketing and handling of LPG (29.9%±8.0%). The NMHC concentrations showed a weekly cycle with the highest levels towards the end of the week and lowest at weekend and beginning of the week, suggesting that both emissions and accumulations process play a key role in building up NMHC levels. The toluene to benzene ratio was used to determine photochemical ageing of the air samples during the 2003 field campaign. The database was divided into periods with similar wind circulation pattern; the results suggest that ageing process within the MCMA is generally suppressed by the amount of fresh emissions.
Cloud-scale model intercomparison of chemical constituent transport in deep convection

Transport and scavenging of chemical constituents in deep convection is important to understanding the composition of the troposphere and therefore chemistry-climate and air quality issues. High resolution cloud chemistry models have been shown to represent convective processing of trace gases quite well. To improve the representation of sub-grid convective transport and wet deposition in large-scale models, general characteristics, such as species mass flux, from the high resolution cloud chemistry models can be used. However, it is important to understand how these models behave when simulating the same storm. The intercomparison described here examines transport of six species. CO and O3, which are primarily transported, show good agreement among models and compare well with observations. Models that included lightning production of NOx reasonably predict NOx mixing ratios in the anvil compared with observations, but the NOx variability is much larger than that seen for CO and O3. Predicted anvil mixing ratios of the soluble species, HNO3, H2O2, and CH2O, exhibit significant differences among models, attributed to different schemes in these models of cloud processing including the role of the ice phase, the impact of cloud-modified photolysis rates on the chemistry, and the representation of the species chemical reactivity. The lack of measurements of these species in the convective outflow region does not allow us to evaluate the model results with observations.