Exploring the potential of nano-Köhler theory to describe the growth of atmospheric molecular clusters by organic vapors using cluster kinetics simulations

Atmospheric new particle formation (NPF) occurs by the formation of nanometer-sized molecular clusters and their subsequent growth to larger particles. NPF involving sulfuric acid, bases and oxidized organic compounds is an important source of atmospheric aerosol particles. One of the mechanisms suggested to depict this process is nano-Köhler theory, which describes the activation of inorganic molecular clusters to growth by a soluble organic vapor. In this work, we studied the capability of nano-Köhler theory to describe the initial growth of atmospheric molecular clusters by simulating the dynamics of a cluster population in the presence of a sulfuric acid–base mixture and an organic compound. We observed nano-Köhler-type activation in our simulations when the saturation ratio of the organic vapor and the ratio between organic and inorganic vapor concentrations were in a suitable range. However, nano-Köhler theory was unable to predict the exact size at which the activation occurred in the simulations. In some conditions, apparent cluster growth rate (GR) started to increase close to the activation size determined from the simulations. Nevertheless, because the behavior of GR is also affected by other dynamic processes, GR alone cannot be used to deduce the cluster growth mechanism.</p

On the formation of sulphuric acid – Amine clusters in varying atmospheric conditions and its influence on atmospheric new particle formation

Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4)

Body Shaping and Volume Restoration: The Role of Hyaluronic Acid

Driven by the rising popularity of minimally invasive techniques, the demand for cosmetic procedures is increasing. Cosmetic body-shaping procedures can be categorized into those that remove tissue and those that add volume. This review focuses on the latter of these categories, particularly on the use of resorbable hyaluronic acid gels specifically developed for minimally invasive volume enhancement. Pilot studies of hyaluronic acid involving its injection to contour various body deformities and its recent use in female breast augmentation are discussed. Injectable hyaluronic acid is effective and well tolerated. It represents an attractive treatment option for volume restoration or augmentation by providing predictable long-lasting results after minimally invasive administration. Alternative treatment options for volume enhancement also are summarized including fat transfer, silicone implants, and the use of injectable nonresorbable products such as silicone, polyalkylimide, and polyacrylamide gels. As patients continue to opt for nonsurgical procedures that offer predictable results, the development of minimally invasive products such as hyaluronic acid is increasingly important

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

4 pages 359-363 in the print version, additional 7 pages online.Peer reviewe

Atmospheric Cluster Dynamics Code: a flexible method for solution of the birth-death equations

The Atmospheric Cluster Dynamics Code (ACDC) is presented and explored. This program was created to study the first steps of atmospheric new particle formation by examining the formation of molecular clusters from atmospherically relevant molecules. The program models the cluster kinetics by explicit solution of the birth–death equations, using an efficient computer script for their generation and the MATLAB ode15s routine for their solution. Through the use of evaporation rate coefficients derived from formation free energies calculated by quantum chemical methods for clusters containing dimethylamine or ammonia and sulphuric acid, we have explored the effect of changing various parameters at atmospherically relevant monomer concentrations. We have included in our model clusters with 0–4 base molecules and 0–4 sulfuric acid molecules for which we have commensurable quantum chemical data. The tests demonstrate that large effects can be seen for even small changes in different parameters, due to the non-linearity of the system. In particular, the temperature and sticking probabilities both have a large impact on all clusters, while the boundary effects (allowing clusters to grow to sizes beyond the largest cluster that the code keeps track of, or forbidding such processes), coagulation sink terms, non-monomer collisions, and monomer concentrations can all have significant effects. Removal of coagulation sink terms prevented the system from reaching the steady state when all the initial cluster concentrations were set to the default value of 1 m[−3], which is probably an effect caused by studying only relatively small cluster sizes

Methane sulfonic acid-enhanced formation of molecular clusters of sulfuric acid and dimethyl amine

Over oceans and in coastal regions, methane sulfonic acid (MSA) is present in substantial concentrations in aerosols and in the gas phase. We present an investigation into the effect of MSA on sulfuric acid- and dimethyl amine (DMA)-based cluster formation rates. From systematic conformational scans and well-tested ab initio methods, we optimise the structures of all MSA_<i>x</i> (H₂SO₄)_yDMA_<i>z</i> clusters where <i>x</i> + <i>y</i> &leq; 3 and <i>z</i> &leq; 2. The resulting thermodynamic data are used in the Atmospheric Cluster Dynamics Code, and the effect of MSA is evaluated by comparing ternary MSA–H₂SO₄–DMA cluster formation rates to binary H₂SO₄–DMA cluster formation rates. Within the range of atmospherically relevant MSA concentrations, we find that MSA may increase cluster formation rates by up to 1 order of magnitude, although typically, the increase will be less than 300 % at 258 K, less than 100 % at 278 K and less than 15 % at 298 K. The results are rationalised by a detailed analysis of the main growth paths of the clusters. We find that MSA-enhanced clustering involves clusters containing one MSA molecule, while clusters containing more than one MSA molecule do not contribute significantly to the growth

Corrigendum to "From quantum chemical formation free energies to evaporation rates" published in Atmos. Chem. Phys., 12, 225–235, 2012

No abstract available

From quantum chemical formation free energies to evaporation rates

Atmospheric new particle formation is an important source of atmospheric aerosols. Large efforts have been made during the past few years to identify which molecules are behind this phenomenon, but the actual birth mechanism of the particles is not yet well known. Quantum chemical calculations have proven to be a powerful tool to gain new insights into the very first steps of particle formation. In the present study we use formation free energies calculated by quantum chemical methods to estimate the evaporation rates of species from sulfuric acid clusters containing ammonia or dimethylamine. We have found that dimethylamine forms much more stable clusters with sulphuric acid than ammonia does. On the other hand, the existence of a very deep local minimum for clusters with two sulfuric acid molecules and two dimethylamine molecules hinders their growth to larger clusters. These results indicate that other compounds may be needed to make clusters grow to larger sizes (containing more than three sulfuric acid molecules)