Ion-induced Nucleation Research Articles

Variation of size-segregated particle number concentrations in wintertime Beijing

Abstract. The spatial and temporal variability of the number size distribution of aerosol particles is an indicator of the dynamic behavior of Beijing's atmospheric pollution cocktail. This variation reflects the strength of different primary and secondary sources, such as traffic and new particle formation, as well as the main processes affecting the particle population. In this paper, we report size-segregated particle number concentrations observed at a newly developed Beijing station during the winter of 2018. Our measurements covered particle number size distributions over the diameter range of 1.5 nm–1 µm (cluster mode, nucleation mode, Aitken mode and accumulation mode), thus being descriptive of a major fraction of the processes taking place in the atmosphere of Beijing. Here we focus on explaining the concentration variations in the observed particle modes, by relating them to the potential aerosol sources and sinks, and on understanding the connections between these modes. We considered haze days and new particle formation event days separately. Our results show that during the new particle formation (NPF) event days increases in cluster mode particle number concentration were observed, whereas during the haze days high concentrations of accumulation mode particles were present. There was a tight connection between the cluster mode and nucleation mode on both NPF event and haze days. In addition, we correlated the particle number concentrations in different modes with concentrations of trace gases and other parameters measured at our station. Our results show that the particle number concentration in all the modes correlated with NOx, which reflects the contribution of traffic to the whole submicron size range. We also estimated the contribution of ion-induced nucleation in Beijing, and we found this contribution to be negligible.

New particle formation in the volcanic eruption plume of the Piton de la Fournaise: specific features from a long-term dataset

Abstract. New particle formation (NPF) is a key atmospheric process which may be responsible for a major fraction of the total aerosol number burden at the global scale, including in particular cloud condensation nuclei (CCN). NPF has been observed in various environments around the world, but some specific conditions, such as those encountered in volcanic plumes, remain poorly documented in the literature. Yet, understanding such natural processes is essential to better define pre-industrial conditions and their variability in climate model simulations. Here we report observations of NPF performed at the high-altitude observatory of Maïdo (2165 m a.s.l., La Réunion Island) between 1 January and 31 December 2015. During this time period, three effusive eruptions of the Piton de la Fournaise, located ∼39 km away from the station, were observed and documented, resulting in 29 d of measurement in volcanic plume conditions to be compared with 250 “non-plume days”. This dataset is, to our knowledge, the largest ever reported for the investigation of NPF in tropospheric volcanic plume conditions, and it allowed for the first time a statistical approach to characterize the process and also assessment of its relevance with respect to non-plume conditions. NPF was observed on 90 % of the plume days vs. 71 % of the non-plume days during the 4 months when the eruptions occurred. The events were on average detected earlier on plume days, most likely benefiting from larger amounts of precursors available at the site prior to nucleation hours. The overall effect of the plume conditions on the particle growth rate was limited. However, with the exception of September, particle formation rates were significantly higher on plume days. The signature of the volcanic plume on the aerosol spectra up to dp=600 nm was further investigated based on the analysis and fitting of the particle size distributions recorded under in-plume and off-plume conditions. The spectra recorded prior to nucleation hours, in the absence of freshly formed particles, featured a significant contribution of particles likely formed via heterogeneous processes at the vent of the volcano (and assimilated to volcanic primary particles) to the concentrations of the two accumulation modes on plume days. Later on in the morning, the concentrations of the nucleation and Aitken modes showed important variations on plume days compared to event days outside of plume conditions. The spectra recorded on event days, under in-plume and off-plume conditions, were further used to provide an average size distribution of the particles of volcanic origin, which clearly highlighted the dominant contribution of secondary over primary particles (93 %) to the total concentration measured on NPF event days within a volcanic plume. In a next step, particular attention was paid to the concentration of particles with dp>50 nm (N50), used as a proxy for potential CCN population. The contribution of secondary particles to the increase in N50 was the most frequent in plume conditions, and the magnitude of the increase was also more important on plume days compared to non-plume days. Finally, in order to further evaluate the effect of volcanic plume conditions on the occurrence of NPF, we analysed the variations of the condensation sink (CS) and [H2SO4], previously reported to play a key role in the process. Over the investigated months, higher CS (calculated prior to nucleation hours) were observed in plume conditions and coincided with high SO2 mixing ratios. Those most likely compensated for the strengthened loss rate of the vapours and favoured the occurrence of NPF, suggesting at the same time a key role of H2SO4 in the process. This last hypothesis was further supported by the correlation between the formation rate of 2 nm particles (J2) and [H2SO4], and by the fair approximation of J2 that was obtained by means of a recent parameterization of the binary nucleation of H2SO4–H2O. This last result demonstrates that in the absence of direct measurements of [H2SO4] and sub-3 nm particle concentrations, estimates of J2 could be fairly estimated from the knowledge of SO2 mixing ratios only. Finally, the use of the parameterization for ion-induced binary nucleation also highlighted the likely significant contribution of ion-induced nucleation for [H2SO4] below ∼8×108 cm−3.

Understanding the nanoparticle formation during electrical wire explosion using a modified moment model

Electrical explosion of wires (EEW) was carried out in an argon atmosphere for the preparation of nanoparticles. Aluminium wires with 0.1 mm diameter and 13 cm length (low mass) and 0.4 mm diameter and 11 cm length (high mass) were used, for which the vaporization energy of the wire was, respectively, far below and comparable to the initial stored energy of the power-supply capacitors. A numerical model was used to study the nanoparticle formation within the exploding wire plasmas. The model is based on a moment method and was modified according to the specific requirements of EEW—rapid expansion of the exploding wire and a high concentration of monomers—to take into consideration the quenching due to mechanical work on the surrounding medium, the energy release during the vapour–liquid phase transition, and the coagulation of liquid particles. The calculation took initial and boundary values from the experimental results and predicted average particle diameters of 36 nm and 116 nm for the low mass and high mass wire respectively, which are in qualitative agreement with the experimental values of 33 nm and 103 nm obtained from SEM images. The nucleation mechanisms including homogeneous nucleation and ion-induced nucleation are discussed in detail; the importance of including the phase transition and coagulation is demonstrated.

Change of Ionization Mechanism in the Welding Fume Plasma from Gas Metal Arc Welding

Ionization mechanisms in welding fumes from gas metal arc welding are studied. Welding fume is a low-temperature thermal plasma with ultra-violet radiation as external ionization source, where ionization occurs via gas particles’ collisions and photoionization. The plasma cooling causes heterogeneous ion-induced nucleation, which provides large number of nuclei. Nucleus number density is much greater than equilibrium number density of charge carriers. Electrons are captured by nuclei. As a result, the dust–ion plasma is formed, in which electron number density is much less than ion and nucleus number densities and it can be neglected. The surface atom ionization and ion recombination becomes predominant processes. Calculation of the plasma component number densities are presented as their evolution during welding fume cooling.

Deducing Proton-Bound Heterodimer Association Energies from Shifts in Ion Mobility Arrival Time Distributions.

Through vapor modification of the counter-current drift gas in an atmospheric pressure drift tube ion mobility spectrometer (IMS), we demonstrate measurement of gas-phase association enthalpies and entropies for select proton-bound heterodimers formed from a phosphonic acid with 2-propanol. Previous efforts to determine gas-phase association thermodynamic properties have relied largely upon lower pressure systems and inference of the relative concentrations of m/ z isolated species. In contrast, the drift tube IMS based approach developed and applied in this study leverages the explicit gas-phase equilibrium that is established within an ion mobility drift cell. The inferred enthalpies and entropies of association are based solely upon monitoring a shift in the arrival time of an ion at different temperatures (and not on the signal intensity or on external instrument drift time calibration). We specifically report the gas-phase Gibbs free energy, enthalpy, and entropy changes for the association of 2-propanol with protonated methyl, ethyl, and propyl phosphonic acid ions (MPA, EPA, PPA) across the 100-175 °C temperature range. For all of these proton-bound heterodimers, the standard enthalpies and entropies of 2-propanol association were negative and positive, respectively. These data indicate that proton-bound heterodimer formation is both enthalpically and entropically favorable, though we find that the magnitude of the standard enthalpy change for vapor association is small (near 1 kcal/mol for all examined heterodimers). Though many prior results (largely obtained with high pressure mass-spectrometry) for other proton-bound organic heterodimer complexes show larger enthalpic favorability and an entropic barrier, our results qualitatively conform to the bulk Kelvin-Thomson-Raoult (KTR) model, which is commonly utilized in describing ion-induced nucleation of a vapor onto a soluble, nanometer scale ion. The KTR model suggests that heterodimer formation due to vapor binding to an ion should be slightly enthalpically favored (due to a larger Thomson effect than the Kelvin effect) and entropically favored because of ion solvation (Raoult's effect). The method presented in this study can be applied to any static-field ion mobility spectrometer and to a wide variety of heterodimers. Due to the ease of implementation and broad applicability, this approach may find consistent use in determining the thermodynamic properties of weakly bound gas-phase heterodimer complexes which are difficult to probe via alternative techniques. Moreover, this renewed implementation of the IMS experiment is directly compatible with soft ionization sources which will enable the characterization of vapor modifier-induced mobility shift experiments for larger molecular complexes.

Ion-Induced Soot Nucleation Using a New Potential for Curved Aromatics

ABSTRACTA potential able to capture the properties and interactions of curved polycyclic aromatic hydrocarbons (cPAHs) was developed and used to investigate the nucleation behavior and structure of nascent soot particles. The flexoelectric charge polarization of cPAHs caused by pentagon integration was included through the introduction of off-site virtual atoms, and enhanced dispersion interaction parameters were fitted. The electric polarization and intermolecular interactions of cPAHs were accurately reproduced compared to ab initio calculations. This potential was used within molecular dynamics simulations to examine the homogeneous and heterogeneous nucleation behavior of the cPAH corannulene and planar PAH coronene across a range of temperatures relevant to combustion. The enhanced interactions between cPAHs and potassium ions resulted in significant and rapid nucleation of stable clusters compared to all other systems, highlighting their importance in soot nucleation. In addition, the resulting cPAH clusters present morphologies distinct from the stacked planar PAH clusters.

Two new submodels for the Modular Earth Submodel System (MESSy): New Aerosol Nucleation (NAN) and small ions (IONS) version 1.0

Abstract. Two new submodels for the Modular Earth Submodel System (MESSy) were developed. The New Aerosol Nucleation (NAN) submodel includes new parameterisations of aerosol particle formation rates published in recent years. These parameterisations include ion-induced nucleation and nucleation of pure organic species. NAN calculates the rate of new particle formation based on the aforementioned parameterisations for aerosol submodels in the ECHAM/MESSy Atmospheric Chemistry (EMAC) model. The ion pair production rate, needed to calculate the ion-induced or ion-mediated nucleation, is described using the new submodel IONS, which provides ion pair production rates for other submodels within the MESSy framework. Both new submodels were tested in EMAC simulations. These simulations showed good agreement with ground-based observations.

A molecular-scale study on the hydration of sulfuric acid-amide complexes and the atmospheric implication

Amides are ubiquitous in atmosphere. However, the role of amides in new particle formation (NPF) is poorly understood. Herein, the interaction of urea and formamide with sulfuric acid (SA) and up to four water (W) molecules has been studied at the M06-2X/6-311++G(3df,3pd) level of theory. The structures and properties of (Formamide)(SA)(W)n (n = 0–4) and (Urea)(SA)(W)n (n = 0–4) clusters were investigated. Results show that the interaction of SA with the CO group of amides plays a more important role in amide clusters compared with the NH2 group. Proton transfer to water molecule become dominant in highly hydrated amide clusters at lower temperatures. There is no proton transfer to CO group in formamide clusters. The Rayleigh light scattering intensities of amide clusters are comparable to that of amine and oxalic acid clusters reported previously. Moreover, unhydrated (Amide)(SA) clusters have similar or even higher ability than hydrated SA clusters to participate in ion-induced nucleation. In comparison with formamide, urea has more interacting sites and its clusters have higher Rayleigh light scattering intensities, larger dipole moment, stronger interaction with SA and lower water affinity. The intermolecular interaction in (Formamide)(SA) is slightly weaker than that of SA dimer, which may be compensated by the high concentration of formamide, thus enabling formamide to participate in initial steps of NPF. This study may bring new insight into the role of amides in initial steps of NPF from molecular scale and could help better understand the properties of amide-containing organic aerosol.

The role of H<sub>2</sub>SO<sub>4</sub>-NH<sub>3</sub> anion clusters in ion-induced aerosol nucleation mechanisms in the boreal forest

Abstract. New particle formation (NPF) provides a large source of atmospheric aerosols, which affect the climate and human health. In recent chamber studies, ion-induced nucleation (IIN) has been discovered as an important pathway of forming particles; however, atmospheric investigation remains incomplete. For this study, we investigated the air anion compositions in the boreal forest in southern Finland for three consecutive springs, with a special focus on H2SO4-NH3 anion clusters. We found that the ratio between the concentrations of highly oxygenated organic molecules (HOMs) and H2SO4 controlled the appearance of H2SO4-NH3 clusters (3<no.S<13): all such clusters were observed when [HOM] ∕ [H2SO4] was smaller than 30. The number of H2SO4 molecules in the largest observable cluster correlated with the probability of ion-induced nucleation (IIN) occurrence, which reached almost 100 % when the largest observable cluster contained six or more H2SO4 molecules. During selected cases when the time evolution of H2SO4-NH3 clusters could be tracked, the calculated ion growth rates exhibited good agreement across measurement methods and cluster (particle) sizes. In these cases, H2SO4-NH3 clusters alone could explain ion growth up to 3 nm (mobility diameter). IIN events also occurred in the absence of H2SO4-NH3, implying that other NPF mechanisms also prevail at this site, most likely involving HOMs. It seems that H2SO4 and HOMs both affect the occurrence of an IIN event, but their ratio ([HOMs] ∕ [H2SO4]) defines the primary mechanism of the event. Since that ratio is strongly influenced by solar radiation and temperature, the IIN mechanism ought to vary depending on conditions and seasons.

Molecular understanding of the interaction of amino acids with sulfuric acid in the presence of water and the atmospheric implication

Amino acids are important components of atmospheric aerosols. Despite the diversity of amino acids structures, however, the role of amino acids with additional non-characteristic functional groups in new particle formation (NPF) has almost remained unexplored. Herein, the interaction of serine (Ser) and threonine (Thr), which feature a hydroxyl group and differ by a methyl-substitution, with sulfuric acid (SA) and up to three water (W) molecules has been investigated at the M06-2X/6-311++G (3df, 3pd) level of theory. The effects of structural differences of amino acids on the structure and properties of clusters were also pointed out. Results show that serine may play more important role in stabilizing sulfuric acid to promote NPF in initial steps compared with threonine, glycine and alanine. Meanwhile, threonine may participate in ion-induced nucleation due to the high dipole moment of (Thr) (SA) isomers. Moreover, the effects of structure differences of amino acids can be seen in several aspects. Firstly, methyl substitution and hydroxyl group of amino acids have great influence on the structure of clusters. Secondly, hydrated (Ser) (SA) and (Tur) (SA) clusters could retain water even at low relative humidity, which may due to the hydroxyl group in serine and threonine. In addition, the Rayleigh light scattering intensities of amino acid-containing clusters are higher than trimethylamine, monoethanolamine and oxalic acid-involved counterparts. The effect of carboxyl group and methyl substitution on optical properties of clusters is also discussed. This study may bring new insight into the role of amino acids with additional non-characteristic functional groups in initial steps of NPF.

Hydration of the methanesulfonate-ammonia/amine complex and its atmospheric implications.

Methanesulfonate (MSA−), found in substantial concentrations in the atmosphere, is expected to enhance aerosol nucleation and the growth of nanoparticles, but the details of methanesulfonate clusters are poorly understood. In this study, MSA− was chosen along with ammonia (NH3) or three common amines and water (H2O) to discuss the roles of ternary homogeneous nucleation and ion-induced nucleation in aerosol formation. We studied the structural characteristics and thermodynamics of the clusters using density functional theory at the PW91PW91/6-311++G(3df,3pd) level. The analysis of noncovalent interactions predicts that the amines can form more stable clusters with MSA− than NH3, in agreement with the results from structures and thermodynamics; however, the enhancement in stability for amines is not large enough to overcome the difference in the concentrations of NH3 and amines under typical atmospheric conditions. In addition, the favorable free energies of formation for the (MSA−)(NH3/amines)(H2O)n (n = 0–3) clusters at 298.15 K show that MSA− could contribute to the aerosol nucleation process with binding NH3/amines and H2O up to n = 3. There are strong temperature and humidity dependences for the formation of complexes; higher humidity and temperature promote the formation of larger hydrates. Finally, for the (MSA−)(NH3/amines)(H2O)n clusters, the evaporation rates were determined to further investigate the atmospheric implications.

The role of ions in new particle formation in the CLOUD chamber

Abstract. The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nanoparticle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e., in conditions in which neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.5 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.5 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.5 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.

Nucleation modeling of the Antarctic stratospheric CN layer and derivation of sulfuric acid profiles

Abstract. Recent analysis of long-term balloon-borne measurements of Antarctic stratospheric condensation nuclei (CN) between July and October showed the formation of a volatile CN layer at 21–27 km altitude in a background of existing particles. We use the nucleation model SAWNUC to simulate these CN in subsiding air parcels and study their nucleation and coagulation characteristics. Our simulations confirm recent analysis that the development of the CN layer can be explained with neutral sulfuric acid–water nucleation and we show that outside the CN layer the measured CN concentrations are well reproduced just considering coagulation and the subsidence of the air parcels. While ion-induced nucleation is expected as the dominating formation process at higher temperatures, it does not play a significant role during the CN layer formation as the charged clusters recombine too fast. Further, we derive sulfuric acid concentrations for the CN layer formation. Our concentrations are about 1 order of magnitude higher than previously presented concentrations as our simulations consider that nucleated clusters have to grow to CN size and can coagulate with preexisting particles. Finally, we calculate threshold sulfuric acid profiles that show which concentration of sulfuric acid is necessary for nucleation and growth to observable size. These threshold profiles should represent upper limits of the actual sulfuric acid outside the CN layer. According to our profiles, sulfuric acid concentrations seem to be below midlatitude average during Antarctic winter but above midlatitude average for the CN layer formation.

Stability and Vapor Pressure of Aqueous Aggregates and Aerosols Containing a Monovalent Ion.

The incidence of charged particles on the nucleation and the stability of aqueous aggregates and aerosols was reported more than a century ago. Many studies have been conducted ever since to characterize the stability, structure, and nucleation barrier of ion-water droplets. Most of these studies have focused on the free-energy surface as a function of cluster size, with an emphasis on the role of ionic charge and radius. This knowledge is fundamental to go beyond the rudimentary ion-induced classical nucleation theory. In the present article, we address this problem from a different perspective, by computing the vapor pressures of (H2O)nLi+ and (H2O)nCl- aggregates using molecular simulations. Our calculations shed light on the structure, the critical size, the range of stability, and the role of ion-water interactions in aqueous clusters. Moreover, they allow one to assess the accuracy of the classical thermodynamic model, highlighting its strengths and weaknesses.

Comparison of the SAWNUC model with CLOUD measurements of sulphuric acid-water nucleation.

Binary nucleation of sulphuric acid‐water particles is expected to be an important process in the free troposphere at low temperatures. SAWNUC (Sulphuric Acid Water Nucleation) is a model of binary nucleation that is based on laboratory measurements of the binding energies of sulphuric acid and water in charged and neutral clusters. Predictions of SAWNUC are compared for the first time comprehensively with experimental binary nucleation data from the CLOUD chamber at European Organization for Nuclear Research. The experimental measurements span a temperature range of 208–292 K, sulphuric acid concentrations from 1·106 to 1·109 cm−3, and distinguish between ion‐induced and neutral nucleation. Good agreement, within a factor of 5, is found between the experimental and modeled formation rates for ion‐induced nucleation at 278 K and below and for neutral nucleation at 208 and 223 K. Differences at warm temperatures are attributed to ammonia contamination which was indicated by the presence of ammonia‐sulphuric acid clusters, detected by an Atmospheric Pressure Interface Time of Flight (APi‐TOF) mass spectrometer. APi‐TOF measurements of the sulphuric acid ion cluster distributions ( (H2SO4)i·HSO4− with i = 0, 1, ..., 10) show qualitative agreement with the SAWNUC ion cluster distributions. Remaining differences between the measured and modeled distributions are most likely due to fragmentation in the APi‐TOF. The CLOUD results are in good agreement with previously measured cluster binding energies and show the SAWNUC model to be a good representation of ion‐induced and neutral binary nucleation of sulphuric acid‐water clusters in the middle and upper troposphere.

Temporal evolution of charged and neutral nanoparticle concentrations during atmospheric new particle formation events and its implications for ion-induced nucleation

Time series of nanoparticle number concentration during new particle formation (NPF) events in the urban environment of Brisbane, Australia, showed that the formation of charged particles often occurred before that of neutral particles. We monitored 241 days during the calendar year 2012 over which NPF events were observed on 108 days. We studied the times at which the charged and neutral particle concentrations in the size range 1.8–3.2 nm reached their peak values and found that they were clearly different in 50 events with the peak neutral particle concentration lagging behind the charged particle concentration during 42 of these events with a mean time lag of 24±12 min. While the charged particles were more likely to form before the neutral particles, once formed, the growth rate of the particles did not depend on their charge. While ion-induced nucleation is not the dominant mechanism of NPF in the atmosphere, our observations suggest that the presence of ions in the atmosphere plays a role that cannot be ignored.

From neutral to new

Atmospheric Particles Many of the particles in the troposphere are formed in situ, but what fraction of all tropospheric particles do they constitute and how exactly are they made? Bianchi et al. report results from a high-altitude research station. Roughly half of the particles were newly formed by the condensation of highly oxygenated multifunctional compounds. A combination of laboratory results, field measurements, and model calculations revealed that neutral nucleation is more than 10 times faster than ion-induced nucleation, that particle growth rates are size-dependent, and that new particle formation occurs during a limited time window. Science , this issue p. [1109][1] [1]: /lookup/doi/10.1126/science.aad5456

New particle formation in the free troposphere: A question of chemistry and timing.

New particle formation (NPF) is the source of over half of the atmosphere's cloud condensation nuclei, thus influencing cloud properties and Earth's energy balance. Unlike in the planetary boundary layer, few observations of NPF in the free troposphere exist. We provide observational evidence that at high altitudes, NPF occurs mainly through condensation of highly oxygenated molecules (HOMs), in addition to taking place through sulfuric acid-ammonia nucleation. Neutral nucleation is more than 10 times faster than ion-induced nucleation, and growth rates are size-dependent. NPF is restricted to a time window of 1 to 2 days after contact of the air masses with the planetary boundary layer; this is related to the time needed for oxidation of organic compounds to form HOMs. These findings require improved NPF parameterization in atmospheric models.

Atmospheric science: Unexpected player in particle formation.

Three studies find that a family of organic compounds affects the formation and initial growth of atmospheric aerosol particles in clean air — with implications for our knowledge of the climate effects of aerosols. See Letters p.521 & 527 The effect of atmospheric aerosols on clouds and the radiative forcing of the climate system remains poorly understood. It is thought that nucleation of aerosol particles from atmospheric vapours rarely proceeds in the absence of sulfuric acid. Now two papers in this week’s Nature point to a previously unappreciated role for highly oxygenated molecules (HOMs) in promoting new particle formation and growth, essentially a mechanism that produces aerosols in the absence of pollution. Jasper Kirkby et al. show that aerosol particles can form as a result of ion-induced nucleation of HOMs in the absence of sulfuric acid under conditions relevant to the atmosphere in the CLOUD chamber at CERN. Jasmin Trostl et al. examined the role of organic vapours in the initial growth of nucleated organic particles in the absence of sulfuric acid in the CERN CLOUD chamber under atmospheric conditions. They find that the organic vapours driving initial growth have extremely low volatilities. With increasing particle size, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility.

Ion-induced nucleation of pure biogenic particles.

Atmospheric aerosols and their effect on clouds are thought to be important for anthropogenic radiative forcing of the climate, yet remain poorly understood. Globally, around half of cloud condensation nuclei originate from nucleation of atmospheric vapours. It is thought that sulfuric acid is essential to initiate most particle formation in the atmosphere, and that ions have a relatively minor role. Some laboratory studies, however, have reported organic particle formation without the intentional addition of sulfuric acid, although contamination could not be excluded. Here we present evidence for the formation of aerosol particles from highly oxidized biogenic vapours in the absence of sulfuric acid in a large chamber under atmospheric conditions. The highly oxygenated molecules (HOMs) are produced by ozonolysis of α-pinene. We find that ions from Galactic cosmic rays increase the nucleation rate by one to two orders of magnitude compared with neutral nucleation. Our experimental findings are supported by quantum chemical calculations of the cluster binding energies of representative HOMs. Ion-induced nucleation of pure organic particles constitutes a potentially widespread source of aerosol particles in terrestrial environments with low sulfuric acid pollution.