Atmospheric aerosols and their effect on clouds are thought to be important for anthropogenic radiative forcing of the climate, yet remain poorly understood¹. Globally, around half of cloud condensation nuclei originate from nucleation of atmospheric vapours². It is thought that sulfuric acid is essential to initiate most particle formation in the atmosphere^3,4, and that ions have a relatively minor role⁵. Some laboratory studies, however, have reported organic particle formation without the intentional addition of sulfuric acid, although contamination could not be excluded^6,7. 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.

About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday¹. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres^2,3. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles⁴, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth^5,6, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer^7,8,9,10. Although recent studies^11,12,13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon², and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory)^2,14, has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown¹⁵ that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10^−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10^−4.5 to 10^−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.

New particle formation has been estimated to produce around half of cloud‐forming particles in the present‐day atmosphere, via gas‐to‐particle conversion. Here we assess the importance of new particle formation (NPF) for both the present‐day and the preindustrial atmospheres. We use a global aerosol model with parametrizations of NPF from previously published CLOUD chamber experiments involving sulfuric acid, ammonia, organic molecules, and ions. We find that NPF produces around 67% of cloud condensation nuclei at 0.2% supersaturation (CCN0.2%) at the level of low clouds in the preindustrial atmosphere (estimated uncertainty range 45–84%) and 54% in the present day (estimated uncertainty range 38–66%). Concerning causes, we find that the importance of biogenic volatile organic compounds (BVOCs) in NPF and CCN formation is greater than previously thought. Removing BVOCs and hence all secondary organic aerosol from our model reduces low‐cloud‐level CCN concentrations at 0.2% supersaturation by 26% in the present‐day atmosphere and 41% in the preindustrial. Around three quarters of this reduction is due to the tiny fraction of the oxidation products of BVOCs that have sufficiently low volatility to be involved in NPF and early growth. Furthermore, we estimate that 40% of preindustrial CCN0.2% are formed via ion‐induced NPF, compared with 27% in the present day, although we caution that the ion‐induced fraction of NPF involving BVOCs is poorly measured at present. Our model suggests that the effect of changes in cosmic ray intensity on CCN is small and unlikely to be comparable to the effect of large variations in natural primary aerosol emissions.

Observations made in the CLOUD chamber at CERN illuminate atmospheric particle formation.

A workshop was held in the framework of the ACCENT (Atmospheric Composition Change – a European Network) Joint Research Programme on "Aerosols" and the Programme on "Access to Laboratory Data". The aim of the workshop was to hold "Gordon Conference" type discussion covering accommodation and reactive uptake of water vapour and trace pollutant gases on condensed phase atmospheric materials. The scope was to review and define the current state of knowledge of accommodation coefficients for water vapour on water droplet and ice surfaces, and uptake of trace gas species on a variety of different surfaces characteristic of the atmospheric condensed phase particulate matter and cloud droplets. Twenty-six scientists participated in this meeting through presentations, discussions and the development of a consensus review. In this review we present an analysis of the state of knowledge on the thermal and mass accommodation coefficient for water vapour on aqueous droplets and ice and a survey of current state-of the-art of reactive uptake of trace gases on a range of liquid and solid atmospheric droplets and particles. The review recommends consistent definitions of the various parameters that are needed for quantitative representation of the range of gas/condensed surface kinetic processes important for the atmosphere and identifies topics that require additional research.