Amines are likely to enhance neutral and ion-induced sulfuric acid-water nucleation in the atmosphere more effectively than ammonia

We have studied the structure and formation thermodynamics of dimer clusters containing H<sub>2</sub>SO<sub>4</sub> or HSO<sub>4</sub><sup>−</sup> together with ammonia and seven different amines possibly present in the atmosphere, using the high-level ab initio methods RI-MP2 and RI-CC2. As expected from e.g. proton affinity data, the binding of all studied amine-H<sub>2</sub>SO<sub>4</sub> complexes is significantly stronger than that of NH<sub>3</sub>•H<sub>2</sub>SO<sub>4</sub>, while most amine-HSO<sub>4</sub><sup>−</sup> complexes are only somewhat more strongly bound than NH<sub>3</sub>•HSO<sub>4</sub><sup>−</sup>. Further calculations on larger cluster structures containing dimethylamine or ammonia together with two H<sub>2</sub>SO<sub>4</sub> molecules or one H<sub>2</sub>SO<sub>4</sub> molecule and one HSO<sub>4</sub><sup>−</sup> ion demonstrate that amines, unlike ammonia, significantly assist the growth of not only neutral but also ionic clusters along the H<sub>2</sub>SO<sub>4</sub> co-ordinate. A sensitivity analysis indicates that the difference in complexation free energies for amine- and ammonia-containing clusters is large enough to overcome the mass-balance effect caused by the fact that the concentration of amines in the atmosphere is probably 2 or 3 orders of magnitude lower than that of ammonia. This implies that amines might be more important than ammonia in enhancing neutral and especially ion-induced sulfuric acid-water nucleation in the atmosphere

CCN activation and cloud processing in simplified sectional aerosol models with low size resolution

International audienceWe investigate the influence of low size resolution, typical to sectional aerosol models in large scale applications, on cloud droplet activation and cloud processing of aerosol particles. A simplified cloud scheme with five approaches to determine the fraction of activated particles is compared with a detailed reference model under different atmospheric conditions. In general, activation approaches which assume a distribution profile within the critical model size sections predict the cloud droplet concentration most accurately under clean and moderately polluted conditions. In such cases, the deviation from the reference simulations is below 15% except for very low updraft velocities. In highly polluted cases, the concentration of cloud droplets is significantly overestimated due to the inability of the simplified scheme to account for the kinetic limitations of the droplet growth. Of the profiles examined, taking into account the local shape of the particle size distribution is the most accurate although in most cases the shape of the profile has little relevance. While the low resolution cloud model cannot reproduce the details of the out-of-the-cloud aerosol size distribution, it captures well the amount of sulphate produced in aqueous-phase reactions as well as the distribution of the sulphate between the cloud droplets. Overall, the simplified cloud scheme with low size resolution performs well for clean and moderately polluted regions that cover most of the Earth's surface and is therefore suitable for large scale models

Measurements of optical properties of atmospheric aerosols in Northern Finland

International audienceThree years of continuous measurements of aerosol optical properties and simultaneous aerosol number size distribution measurements at Pallas GAW station, a remote subarctic site in the northern border of the boreal forest zone, have been analysed. The scattering coefficient at 550 nm varied from 0.2 to 94.4 Mm?1 with an average of 7.1±8.6 Mm?1. Both the scattering and backscattering coefficients had a clear seasonal cycle with an autumn minimum and a 4?5 times higher summer maximum. The scattering was dominated by submicron aerosols and especially so during late summer and autumn. The Ångström exponent had a clear seasonal pattern with maximum values in late summer and minimum values during wintertime. The highest hemispheric backscattering fraction values were observed in autumn, indicating clean air with few scattering particles and a particle size distribution strongly dominated by ultrafine particles. To analyse the influence of air mass origin on the aerosol optical properties a trajectory climatology was applied to the Pallas aerosol data. The most polluted trajectory patterns represented air masses from the Kola Peninsula, Scandinavia and Russia as well as long-range transport from Britain and Eastern Europe. These air masses had the largest average scattering and backscattering coefficients for all seasons. Higher than average values of the Ångström exponent were also observed in connection with transport from these areas

Production of neutral molecular clusters by controlled neutralization of mobility standards

Measuring aerosols and molecular clusters below the 3 nm size limit is essential to increase our understanding of new particle formation. Instruments for the detection of sub-3 nm aerosols and clusters exist and need to be carefully calibrated and characterized. So far calibrations and laboratory tests have been carried out using mainly electrically charged aerosols, as they are easier to handle experimentally. However, the charging state of the cluster is an important variable to take into account. Furthermore, instrument characterization performed with charged aerosols could be biased, preventing a correct interpretation of data when electrically neutral sub-3 nm aerosols are involved. This article presents the first steps to generate electrically neutral molecular clusters as standards for calibration. We show two methods: One based on the neutralization of well-known molecular clusters (mobility standards) by ions generated in a switchable aerosol neutralizer. The second is based on the controlled neutralization of mobility standards with mobility standards of opposite polarity in a recombination cell. We highlight the challenges of these two techniques and, where possible, point out solutions. In addition, we give an outlook on the next steps toward generating well-defined neutral molecular clusters with a known chemical composition and concentration.Peer reviewe

Fatty acids on continental sulfate aerosol particles

Published 2005 American Geophysical Union. Reproduced by permission of American Geophysical Union.Surface analyses of atmospheric aerosols from different continental sources, such as forest fires and coal and straw burning, show that organic surfactants are found on such aerosols. The predominant organic species detected by time-of-flight secondary ion mass spectrometry on the sulfate aerosols are fatty acids of different carbon chain length up to the C32 acid. These observations are consistent with literature accounts of functional group analysis of bulk samples, but this is the first direct evidence of fatty acid films on the surface of sulfate aerosols. Surface analysis leads to the conclusion that fatty acid films on continental aerosols may be more common than has been previously suggested

The contribution of boundary layer nucleation events to total particle concentrations on regional and global scales

International audienceThe contribution of boundary layer (BL) nucleation events to total particle concentrations on the global scale has been studied by including a new particle formation mechanism in a global aerosol microphysics model. The mechanism is based on an analysis of extensive observations of particle formation in the BL at a continental surface site. It assumes that molecular clusters form at a rate proportional to the gaseous sulfuric acid concentration to the power of 1. The formation rate of 3 nm diameter observable particles is controlled by the cluster formation rate and the existing particle surface area, which acts to scavenge condensable gases and clusters during growth. Modelled sulfuric acid vapour concentrations, particle formation rates, growth rates, coagulation loss rates, peak particle concentrations, and the daily timing of events in the global model agree well with observations made during a 22-day period of March 2003 at the SMEAR II station in Hyytiälä, Finland. The nucleation bursts produce total particle concentrations (>3 nm diameter) often exceeding 104 cm?3, which are sustained for a period of several hours around local midday. The predicted global distribution of particle formation events broadly agrees with what is expected from available observations. Over relatively clean remote continental locations formation events can sustain mean total particle concentrations up to a factor of 8 greater than those resulting from anthropogenic sources of primary organic and black carbon particles. However, in polluted continental regions anthropogenic primary particles dominate particle number and formation events lead to smaller enhancements of up to a factor of 2. Our results therefore suggest that particle concentrations in remote continental regions are dominated by nucleated particles while concentrations in polluted continental regions are dominated by primary particles. The effect of BL particle formation over tropical regions and the Amazon is negligible. These first global particle formation simulations reveal some interesting sensitivities. We show, for example, that significant reductions in primary particle emissions may lead to an increase in total particle concentration because of the coupling between particle surface area and the rate of new particle formation. This result suggests that changes in emissions may have a complicated effect on global and regional aerosol properties. Overall, our results show that new particle formation is a significant component of the aerosol particle number budget

Parameterization of ion-induced nucleation rates based on ambient observations

Atmospheric ions participate in the formation of new atmospheric aerosol particles, yet their exact role in this process has remained unclear. Here we derive a new simple parameterization for ion-induced nucleation or, more precisely, for the formation rate of charged 2-nm particles. The parameterization is semi-empirical in the sense that it is based on comprehensive results of one-year-long atmospheric cluster and particle measurements in the size range ~1–42 nm within the EUCAARI (European Integrated project on Aerosol Cloud Climate and Air Quality interactions) project. Data from 12 field sites across Europe measured with different types of air ion and cluster mobility spectrometers were used in our analysis, with more in-depth analysis made using data from four stations with concomitant sulphuric acid measurements. The parameterization is given in two slightly different forms: a more accurate one that requires information on sulfuric acid and nucleating organic vapor concentrations, and a simpler one in which this information is replaced with the global radiation intensity. These new parameterizations are applicable to all large-scale atmospheric models containing size-resolved aerosol microphysics, and a scheme to calculate concentrations of sulphuric acid, condensing organic vapours and cluster ions

An improved criterion for new particle formation in diverse atmospheric environments

A dimensionless theory for new particle formation (NPF) was developed, using an aerosol population balance model incorporating recent developments in nucleation rates and measured particle growth rates. Based on this theoretical analysis, it was shown that a dimensionless parameter <i>L</i><sub>Γ</sub>, characterizing the ratio of the particle scavenging loss rate to the particle growth rate, exclusively determined whether or not NPF would occur on a particular day. This parameter determines the probability that a nucleated particle will grow to a detectable size before being lost by coagulation with the pre-existing aerosol. Cluster-cluster coagulation was shown to contribute negligibly to this survival probability under conditions pertinent to the atmosphere. Data acquired during intensive measurement campaigns in Tecamac (MILAGRO), Atlanta (ANARChE), Boulder, and Hyytiälä (QUEST II, QUEST IV, and EUCAARI) were used to test the validity of <i>L</i><sub>Γ</sub> as an NPF criterion. Measurements included aerosol size distributions down to 3 nm and gas-phase sulfuric acid concentrations. The model was applied to seventy-seven NPF events and nineteen non-events (characterized by growth of pre-existing aerosol without NPF) measured in diverse environments with broad ranges in sulfuric acid concentrations, ultrafine number concentrations, aerosol surface areas, and particle growth rates (nearly two orders of magnitude). Across this diverse data set, a nominal value of <i>L</i><sub>Γ</sub>=0.7 was found to determine the boundary for the occurrence of NPF, with NPF occurring when <i>L</i><sub>Γ</sub><0.7 and being suppressed when <i>L</i><sub>Γ</sub>>0.7. Moreover, nearly 45% of measured <i>L</i><sub>Γ</sub> values associated with NPF fell in the relatively narrow range of 0.1<<i>L</i><sub>Γ</sub><0.3