SUPPLEMENTARY INFORMATION Typical measurement sequenceThe nucleation rates (J cm −3 s −1 ) are measured under neutral (J n ), galactic cosmic ray (J gcr ) or charged pion beam (J ch ) conditions. For J gcr a beam stopper blocks the pions and the chamber is irradiated by GCRs together with a small parasitic component of penetrating beam muons, whereas, for J ch , the beam stopper is opened and the pion beam is normally set to a time-averaged rate of (5 − 6) · 10 4 s −1 . Neutral nucleation rates are measured

Abstract. We present comprehensive results on continuous atmospheric cluster and particle measurements in the size range ∼1-42 nm within the European Integrated project on Aerosol Cloud Climate and Air Quality interactions (EU-CAARI) project. We focused on characterizing the spatial and temporal variation of new particle formation events and Correspondence to: H. E. Manninen (hanna.manninen@helsinki.fi) relevant particle formation parameters across Europe. Different types of air ion and cluster mobility spectrometers were deployed at 12 field sites across Europe from March 2008 to May 2009. The measurements were conducted in a wide variety of environments, including coastal and continental locations as well as sites at different altitudes (both in the boundary layer and the free troposphere). New particle formation events were detected at all of the 12 field sites during the year-long measurement period. From the data, Published by Copernicus Publications on behalf of the European Geosciences Union. 7908H. E. Manninen et al.: EUCAARI ion spectrometer measurements nucleation and growth rates of newly formed particles were determined for each environment. In a case of parallel ion and neutral cluster measurements, we could also estimate the relative contribution of ion-induced and neutral nucleation to the total particle formation. The formation rates of charged particles at 2 nm accounted for 1-30% of the corresponding total particle formation rates. As a significant new result, we found out that the total particle formation rate varied much more between the different sites than the formation rate of charged particles. This work presents, so far, the most comprehensive effort to experimentally characterize nucleation and growth of atmospheric molecular clusters and nanoparticles at ground-based observation sites on a continental scale.

This review is based on ca. 260 publications, 93 of which included data on the temporal and spatial variation of the concentration of small ions (<1.6 nm in diameter) especially in the lower troposphere, chemical composition, or formation and growth rates of sub-3 nm ions. This information was collected on tables and figures. The small ions exist all the time in the atmosphere, and the average concentrations of positive and negative small ions are typically 200–2500 cm⁻³. However, concentrations up to 5000 cm⁻³ have been observed. The results are in agreement with observations of ion production rates in the atmosphere. We also summarised observations on the conversion of small ions to intermediate ions, which can act as embryos for new atmospheric aerosol particles. Those observations include the formation rates (<i>J</i>₂[ion]) of 2-nm intermediate ions, growth rates (GR[ion]) of sub-3 nm ions, and information on the chemical composition of the ions. Unfortunately, there were only a few studies which presented <i>J</i>₂[ion] and GR[ion]. Based on the publications, the formation rates of 2-nm ions were 0–1.1 cm⁻³ s⁻¹, while the total 2-nm particle formation rates varied between 0.001 and 60 cm⁻³ s⁻¹. Due to small changes in <i>J</i>₂[ion], the relative importance of ions in 2-nm particle formation was determined by the large changes in <i>J</i>₂[tot], and, accordingly the contribution of ions increased with decreasing <i>J</i>₂[tot]. Furthermore, small ions were observed to activate for growth earlier than neutral nanometer-sized particles and at lower saturation ratio of condensing vapours