Henning Henschel

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

Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere. It is thought that amines may enhance nucleation, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.

Hydration of atmospherically relevant molecular clusters: computational chemistry and classical thermodynamics.

Formation of new particles through clustering of molecules from condensable vapors is a significant source for atmospheric aerosols. The smallest clusters formed in the very first steps of the condensation process are, however, not directly observable by experimental means. We present here a comprehensive series of electronic structure calculations on the hydrates of clusters formed by up to four molecules of sulfuric acid, and up to two molecules of ammonia or dimethylamine. Though clusters containing ammonia, and certainly dimethylamine, generally exhibit lower average hydration than the pure acid clusters, populations of individual hydrates vary widely. Furthermore, we explore the predictions obtained using a thermodynamic model for the description of these hydrates. The similar magnitude and trends of hydrate formation predicted by both methods illustrate the potential of combining them to obtain more comprehensive models. The stabilization of some clusters relative to others due to their hydration is highly likely to have significant effects on the overall processes that lead to formation of new particles in the atmosphere.

Effect of ions on sulfuric acid-water binary particle formation: 2. Experimental data and comparison with QC-normalized classical nucleation theory

We report comprehensive, demonstrably contaminant-free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion-induced pathways conducted in the European Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface-time of flight-mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (10^5 to 10^9  mol cm^(−3)), relative humidity (11% to 58%), temperature (207 K to 299 K), and total ion concentration (0 to 6800 ions cm^(−3)). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3 nm to 3.2 nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC-normalized CNT), which is described in a companion paper. The formation rates predicted by the QC-normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion-induced) sulfuric acid-water system. Formation rates increase with RH, sulfuric acid, and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions, neutral particle formation dominates at low temperatures, while ion-induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC-normalized CNT as a powerful tool to study neutral and ion-induced binary particle formation in atmospheric modeling.

Molecular-scale evidence of aerosol particle formation via sequential addition of HIO3

Homogeneous nucleation and subsequent cluster growth leads to the formation of new aerosol particles in the atmosphere. The nucleation of sulfuric acid and organic vapours is thought to be responsible for the formation of new particles over continents, whereas iodine oxide vapours have been implicated in particle formation over coastal regions. The molecular clustering pathways that are involved in atmospheric particle formation have been elucidated in controlled laboratory studies of chemically simple systems, but direct molecular-level observations of nucleation in atmospheric field conditions that involve sulfuric acid, organic or iodine oxide vapours have yet to be reported. Here we present field data from Mace Head, Ireland, and supporting data from northern Greenland and Queen Maud Land, Antarctica, that enable us to identify the molecular steps involved in new particle formation in an iodine-rich, coastal atmospheric environment. We find that the formation and initial growth process is almost exclusively driven by iodine oxoacids and iodine oxide vapours, with average oxygen-to-iodine ratios of 2.4 found in the clusters. On the basis of this high ratio, together with the high concentrations of iodic acid (HIO3) observed, we suggest that cluster formation primarily proceeds by sequential addition of HIO3, followed by intracluster restructuring to I2O5 and recycling of water either in the atmosphere or on dehydration. Our study provides ambient atmospheric molecular-level observations of nucleation, supporting the previously suggested role of iodine-containing species in the formation of new aerosol particles, and identifies the key nucleating compound.

Computational Study on the Effect of Hydration on New Particle Formation in the Sulfuric Acid/Ammonia and Sulfuric Acid/Dimethylamine Systems.

The formation of new particles through condensation from the gas phase is an important source of atmospheric aerosols. The properties of the electrically neutral clusters formed in the very first steps of the condensation process are, however, not directly observable by experimental means. We present here electronic structure calculations on the hydrates of clusters of three molecules of sulfuric acid and three molecules of ammonia or dimethylamine. On the basis of the results of these new calculations together with previously published material we simulate the influence of hydration on the dynamic processes involved in particle formation. Most strongly affected by hydration and most important as a mediator for the effect on particle formation rates are the evaporation rates of clusters. The results give an estimate of the sensitivity of the atmospheric particle formation rate for humidity. The particle formation rate can change approximately two orders of magnitude in either direction due to hydration; the net effect, however, is highly dependent on the exact conditions.

Structures, Hydration, and Electrical Mobilities of Bisulfate Ion-Sulfuric Acid-Ammonia/Dimethylamine Clusters: A Computational Study.

Despite the well-established role of small molecular clusters in the very first steps of atmospheric particle formation, their thermochemical data are still not completely available due to limitation of the experimental techniques to treat such small clusters. We have investigated the structures and the thermochemistry of stepwise hydration of clusters containing one bisulfate ion, sulfuric acid, base (ammonia or dimethylamine), and water molecules using quantum chemical methods. We found that water facilitates proton transfer from sulfuric acid or the bisulfate ion to the base or water molecules, and depending on the hydration level, the sulfate ion was formed in most of the base-containing clusters. The calculated hydration energies indicate that water binds more strongly to ammonia-containing clusters than to dimethylamine-containing and base-free clusters, which results in a wider hydrate distribution for ammonia-containing clusters. The electrical mobilities of all clusters were calculated using a particle dynamics model. The results indicate that the effect of humidity is negligible on the electrical mobilities of molecular clusters formed in the very first steps of atmospheric particle formation. The combination of the results of this study with those previously published on the hydration of neutral clusters by our group provides a comprehensive set of thermochemical data on neutral and negatively charged clusters containing sulfuric acid, ammonia, or dimethylamine.

Comment on ‘Enhancement in the production of nucleating clusters due to dimethylamine and large uncertainties in the thermochemistry of amine-enhanced nucleation’ by Nadykto et al., Chem. Phys. Lett. 609 (2014) 42–49

Abstract We comment on a study by Nadykto et al. recently published in this journal. Earlier work from our group has been misrepresented in this study, and we feel that the claims made need to be amended. Also the analysis of Nadykto et al. concerning the implications of their own density functional calculations is incomplete. We present cluster formation simulations allowing more conclusions to be drawn from their data, and also compare them to recent experimental results not cited in their work.

Effect of Hydration and Base Contaminants on Sulfuric Acid Diffusion Measurement: A Computational Study

We used quantum chemical formation free energies of hydrated sulfuric acid-containing molecular clusters and a dynamic model to simulate a flow tube measurement, and determined the effective diffusion coefficient of sulfuric acid as a function of relative humidity. This type of measurement was performed by Hanson and Eisele, who presented and applied a fitting method to obtain equilibrium constants K1 and K2 for the formation of sulfuric acid mono- and dihydrates, respectively, from the experimentally determined diffusion coefficients. The fit is derived assuming that only H2SO4 molecules hydrated by up to two water molecules are present. To study the sensitivity of the results to this assumption, we implemented the same fit to the modeled diffusion coefficient data, computed including also larger H2SO4 hydrates with more than two waters. We show that according to quantum chemical equilibrium constants, the larger hydrates are likely to be present in nonnegligible amounts, which affects the effective diffusion coefficient. This results in the fitted value obtained for K1 being lower and for K2 being higher than the actual values. The results are further altered if contaminant base molecules, such as amines, capable of binding to H2SO4 molecules, are able to enter the system, for example, with the water vapor. The magnitude and direction of the effect of the contaminants depends not only on the contaminant concentration, but also on the H2SO4 concentration and on the hygroscopicity of the H2SO4–base clusters. Copyright 2014 American Association for Aerosol Research

New particle formation from sulfuric acid and amines: Comparison of monomethylamine, dimethylamine, and trimethylamine

Amines are bases that originate from both anthropogenic and natural sources, and they are recognized as candidates to participate in atmospheric aerosol particle formation together with sulfuric acid. Monomethylamine, dimethylamine, and trimethylamine (MMA, DMA, and TMA, respectively) have been shown to enhance sulfuric acid-driven particle formation more efficiently than ammonia, but both theory and laboratory experiments suggest that there are differences in their enhancing potentials. However, as quantitative concentrations and thermochemical properties of different amines remain relatively uncertain, and also for computational reasons, the compounds have been treated as a single surrogate amine species in large-scale modeling studies. In this work, the differences and similarities of MMA, DMA, and TMA are studied by simulations of molecular cluster formation from sulfuric acid, water, and each of the three amines. Quantum chemistry-based cluster evaporation rate constants are applied in a cluster population dynamics model to yield cluster concentrations and formation rates at boundary layer conditions. While there are differences, for instance, in the clustering mechanisms and cluster hygroscopicity for the three amines, DMA and TMA can be approximated as a lumped species. Formation of nanometer-sized particles and its dependence on ambient conditions is roughly similar for these two: both efficiently form clusters with sulfuric acid, and cluster formation is rather insensitive to changes in temperature and relative humidity. Particle formation from sulfuric acid and MMA is weaker and significantly more sensitive to ambient conditions. Therefore, merging MMA together with DMA and TMA introduces inaccuracies in sulfuric acid-amine particle formation schemes.

New Parameterizations for Neutral and Ion-Induced Sulfuric Acid-Water Particle Formation in Nucleation and Kinetic Regimes

We have developed new parameterizations of electrically neutral homogeneous and ion-induced sulfuric acid - water particle formation for large ranges of environmental conditions, based on an improved model that has been validated against a particle formation rate data set produced by Cosmics Leaving OUtdoor Droplets (CLOUD) experiments at CERN. The model uses a thermodynamically consistent version of the Classical Nucleation Theory normalized using quantum chemical data. Unlike the earlier parameterizations for H 2 SO 4 -H 2 O nucleation, the model is applicable to extreme dry conditions where the one-component sulfuric acid limit is approached. Parameterizations are presented for the critical cluster sulfuric acid mole fraction, the critical cluster radius, the total number of molecules in the critical cluster, and the particle formation rate. If the critical cluster contains only one sulfuric acid molecule, a simple formula for kinetic particle formation can be used: this threshold has also been parameterized. The parameterization for electrically neutral particle formation is valid for the following ranges: temperatures 165-400 K, sulfuric acid concentrations 10 4 -10 13 cm −3 and relative humidities 0.001-100%. The ion-induced particle formation parameterization is valid for temperatures 195-400 K, sulfuric acid concentrations 10 4 -10 16 cm −3 and relative humidities 10 −5 -100%. The new parameterizations are thus applicable for the full range of conditions in the Earths atmosphere relevant for binary sulfuric acid - water particle formation, including both tropospheric and stratospheric conditions. They are also suitable for describing particle formation in the atmosphere of Venus.