The role of atmospheric ions in aerosol nucleation:a review

Atmospheric aerosols affect climate and yet the reason for many observed events of new aerosol formation is not understood. One of the theories put forward to explain these events is that the presence of ions can enhance the formation of aerosols. The theory is called Ion Induced Nucleation and in this paper the state of observations, theory and experiments within the field will be reviewed. While evidence for Ion Induced Nucleation is accumulating the exact mechanism is still not known and more research is required to understand and quantify the effect

Model of optical response of marine aerosols to Forbush decreases

In order to elucidate the effect of galactic cosmic rays on cloud formation, we investigate the optical response of marine aerosols to Forbush decreases – abrupt decreases in galactic cosmic rays – by means of modeling. We vary the nucleation rate of new aerosols, in a sectional coagulation and condensation model, according to changes in ionization by the Forbush decrease. From the resulting size distribution we then calculate the aerosol optical thickness and Angstrom exponent, for the wavelength pairs 350, 450 nm and 550, 900 nm. In the cases where the output parameters from the model seem to compare best with atmospheric observations we observe, for the shorter wavelength pair, a change in Angstrom exponent, following the Forbush Decrease, of −6 to +3%. In some cases we also observe a delay in the change of Angstrom exponent, compared to the maximum of the Forbush decrease, which is caused by different sensitivities of the probing wavelengths to changes in aerosol number concentration and size. For the long wavelengths these changes are generally smaller. The types and magnitude of change is investigated for a suite of nucleation rates, condensable gas production rates, and aerosol loss rates. Furthermore we compare the model output with observations of 5 of the largest Forbush decreases after year 2000. For the 350, 450 nm pair we use AERONET data and find a comparable change in signal while the Angstrom Exponent is lower in the model than in the data, due to AERONET being mainly sampled over land. For 550, 900 nm we compare with both AERONET and MODIS and find little to no response in both model and observations. In summary our study shows that the optical properties of aerosols show a distinct response to Forbush Decreases, assuming that the nucleation of fresh aerosols is driven by ions. Shorter wavelengths seem more favorable for observing these effects and great care should be taken when analyzing observations, in order to avoid the signal being drowned out by noise

Measurement of the charging state of 4-70 nm aerosols

The charging state of aerosols in an 8 m3 reaction chamber was measured using an electrostatic classifier with a condensation particle counter at different levels of ionization in the chamber. By replacing the Kr-85 neutralizer in the classifier with a radioactively neutral dummy we were able to measure only the aerosols that were charged inside our reaction chamber. These measurements were then compared with measurements using the neutralizer to get the charging state of the aerosols, which refers to the charged fraction of the aerosols compared to an equilibrium charge distribution. Charging states were measured for both positively and negatively charged aerosols while the ionization in the chamber was varied using external gamma sources. We find that the negatively charged aerosols were overcharged (relative to the equilibrium) by up to about a factor of 10 below 10 nm and at 16±2% from 10 to 70 nm. At higher levels of radiation on the chamber the smaller aerosols were less overcharged while the large aerosols were more overcharged (23±2%). For the positively charged aerosols only the smallest aerosols were overcharged while those over 10 nm were undercharged (relative to the equilibrium) by 21±3%. Increasing the radiation on the chamber increased the undercharge above 10 nm to 25±2% while the overcharge below 10 nm disappeared. The split between positive and negative charges above 10 nm can be explained by differences in mobility of small negative and positive ions. The overcharge below 10 nm can be explained by ions participating in the formation of aerosols of both signs, while the reduction in this overcharge at higher levels of ionization may be explained by faster recombination

The response of clouds and aerosols to cosmic ray decreases

A method is developed to rank Forbush decreases (FDs) in the galactic cosmic ray radiation according to their expected impact on the ionization of the lower atmosphere. Then a Monte Carlo bootstrap-based statistical test is formulated to estimate the significance of the apparent response in physical and microphysical cloud parameters to FDs. The test is subsequently applied to one ground-based and three satellite-based data sets. Responses (&gt;95%) to FDs are found in the following parameters of the analyzed data sets. AERONET: &#xC5;ngstr&#xF6;m exponent (cloud condensation nuclei changes), SSM/I: liquid water content, International Satellite Cloud Climate Project (ISCCP): total, high, and middle, IR-detected clouds over the oceans, Moderate Resolution Imaging Spectroradiometer (MODIS): cloud effective emissivity, cloud optical thickness, liquid water, cloud fraction, liquid water path, and liquid cloud effective radius. Moreover, the responses in MODIS are found to correlate positively with the strength of the FDs, and the signs and magnitudes of the responses agree with model-based expectations. The effect is mainly seen in liquid clouds. An impact through changes in UV-driven photo chemistry is shown to be negligible and an impact via UV absorption in the stratosphere is found to have no effect on clouds. The total solar irradiance has a relative decrease in connection with FDs of the order of 10&#x2212;3, which is too small to have a thermodynamic impact on timescales of a few&#xA0;days. The results demonstrate that there is a real influence of FDs on clouds probably through ions.</p

Structures and reaction rates of the gaseous oxidation of SO₂ by an O₋₃ (H₂O)₀₋₅ cluster – a density functional theory investigation

Based on density functional theory calculations we present a study of the gaseous oxidation of SO₂ to SO₃ by an anionic O₃^&minus;(H₂O)_<i>n</i> cluster, <i>n</i> = 0–5. The configurations of the most relevant reactants, transition states, and products are discussed and compared to previous findings. Two different classes of transition states have been identified. One class is characterised by strong networks of hydrogen bonds, very similar to the reactant complexes. The other class is characterised by sparser structures of hydration water and is stabilised by high entropy. At temperatures relevant for atmospheric chemistry, the most energetically favourable class of transition states vary with the number of water molecules attached. A kinetic model is utilised, taking into account the most likely outcomes of the initial SO₂ O₃^&minus;(H₂O)_<i>n</i> collision complexes. This model shows that the reaction takes place at collision rates regardless of the number of water molecules involved. A lifetime analysis of the collision complexes supports this conclusion. Hereafter, the thermodynamics of water and O₂ condensation and evaporation from the product SO₃^&minus;O₂(H₂O)_<i>n</i> cluster is considered and the final products are predicted to be O₂SO₃^&minus; and O₂SO₃^&minus;(H₂O)₁. The low degree of hydration is rationalised through a charge analysis of the relevant complexes. Finally, the thermodynamics of a few relevant reactions of the O₂SO₃^&minus; and O₂SO₃^&minus;(H₂O)₁ complexes are considered

Ab initio studies of O2-(H2O)n and O3-(H2O)n anionic molecular clusters, n≤12

An ab initio study of gaseous clusters of O₂^&minus; and O₃^&minus; with water is presented. Based on thorough scans of configurational space, we determine the thermodynamics of cluster growth. The results are in good agreement with benchmark computational methods and existing experimental data. We find that anionic O₂^&minus;(H₂O)_<i>n</i> and O₃^&minus;(H₂O)_<i>n</i> clusters are thermally stabilized at typical atmospheric conditions for at least <i>n</i> = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H₂O is due to normal hydrogen bonding. Although clustering up to 12 H₂O, we find that the O₂ and O₃ anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O₂^&minus; and O₃^&minus; speicies are thus accessible for further reactions. We consider the distributions of cluster sizes as function of altitude before finally, the thermodynamics of a few relevant cluster reactions are considered

An isotopic analysis of ionising radiation as a source of sulphuric acid

Sulphuric acid is an important factor in aerosol nucleation and growth. It has been shown that ions enhance the formation of sulphuric acid aerosols, but the exact mechanism has remained undetermined. Furthermore some studies have found a deficiency in the sulphuric acid budget, suggesting a missing source. In this study the production of sulphuric acid from SO&lt;sub&gt;2&lt;/sub&gt; through a number of different pathways is investigated. The production methods are standard gas phase oxidation by OH radicals produced by ozone photolysis with UV light, liquid phase oxidation by ozone, and gas phase oxidation initiated by gamma rays. The distributions of stable sulphur isotopes in the products and substrate were measured using isotope ratio mass spectrometry. All methods produced sulphate enriched in &lt;sup&gt;34&lt;/sup&gt;S and we find an enrichment factor (&amp;delta;&lt;sup&gt;34&lt;/sup&gt;S) of 8.7 ± 0.4&amp;permil; (1 standard deviation) for the UV-initiated OH reaction. Only UV light (Hg emission at 253.65 nm) produced a clear non-mass-dependent excess of &lt;sup&gt;33&lt;/sup&gt;S. The pattern of isotopic enrichment produced by gamma rays is similar, but not equal, to that produced by aqueous oxidation of SO&lt;sub&gt;2&lt;/sub&gt; by ozone. This, combined with the relative yields of the experiments, suggests a mechanism in which ionising radiation may lead to hydrated ion clusters that serve as nanoreactors for S(IV) to S(VI) conversion