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Publisher Copyright: © 2021 Mao Xiao et al. New particle formation (NPF) is a significant source of atmospheric particles, affecting climate and air quality. Understanding the mechanisms involved in urban aerosols is important to develop effective mitigation strategies. However, NPF rates reported in the polluted boundary layer span more than 4 orders of magnitude, and the reasons behind this variability are the subject of intense scientific debate. Multiple atmospheric vapours have been postulated to participate in NPF, including sulfuric acid, ammonia, amines and organics, but their relative roles remain unclear. We investigated NPF in the CLOUD chamber using mixtures of anthropogenic vapours that simulate polluted boundary layer conditions. We demonstrate that NPF in polluted environments is largely driven by the formation of sulfuric acid-base clusters, stabilized by the presence of amines, high ammonia concentrations and lower temperatures. Aromatic oxidation products, despite their extremely low volatility, play a minor role in NPF in the chosen urban environment but can be important for particle growth and hence for the survival of newly formed particles. Our measurements quantitatively account for NPF in highly diverse urban environments and explain its large observed variability. Such quantitative information obtained under controlled laboratory conditions will help the interpretation of future ambient observations of NPF rates in polluted atmospheres.

New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.

Article, The concentrations of neutral and charged sub-3nm clusters and their connection to new particle formation (NPF) were investigated during the PEGASOS campaign (7 June–9 July 2012) at the San Pietro Capofiume measurement station in the Po Valley, Italy. Continuous high concentrations of sub-3nm clusters were detected during the measurement period, although the condensation sink was relatively high (median value 1.1 × 10−2 s−1). The median cluster concentrations were 2140 and 7980 cm−3 in the size bins of 1.5–1.8 and 1.8–3 nm, and the majority of them were electrically neutral. NPF events were observed during the measurement period frequently, on 86 % of the days. The median growth rates of clusters during the events were 4.3, 6.0 and 7.2 nm h−1 in the size ranges of 1.5–3, 3–7 and 7–20 nm. The median formation rate of 1.6 nm clusters was high, 45 cm−3 s−1, and it exceeded the median formation rate of 2 nm clusters by 1 order of magnitude. The ion-induced nucleation fraction was low; the median values were 0.7 % at 1.6 nm and 3.0 % at 2 nm. On NPF event days the neutral cluster concentration had a maximum around 09:00 (local winter time), which was absent on a non-event day. The increase in the cluster concentrations in the morning coincided with the increase in the boundary layer height. At the same time radiation, temperature and SO2 concentration increased, and RH and condensation sink decreased. The concentrations of neutral and charged clusters were observed to have a positive correlation with sulfuric acid proxy, indicating the significance of sulfuric acid for the cluster formation in San Pietro Capofiume. The condensation sink had a negative correlation with the concentration of charged clusters but no clear relation to the neutral cluster concentration. This finding, together with back-trajectory analysis, suggests that the precursor vapors of the clusters and background aerosol particles, acting as their sink, have possibly originated from the same sources, including e.g., power plants and industrial areas in the Po Valley., published version, peerReviewed

It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1–2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 °C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and −25 °C). Most negative HOM clusters include a nitrate (NO3−) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH4+) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ∼ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (−25 °C), the presence of C30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.

Atmospheric oxidation is an important phenomenon which produces large quantities of low-volatility compounds such as sulfuric acid and oxidized organic compounds. Such species may be involved in the nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate α-pinene, the most abundant monoterpene globally, and its oxidation products formed through ozonolysis in the Cosmic Leaving OUtdoor Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H2), we were able to investigate the formation of highly oxygenated molecules (HOMs) purely driven by ozonolysis and study the oxidation of sulfur dioxide (SO2) driven by stabilized Criegee intermediates (sCIs). We measured the concentrations of HOM and sulfuric acid with a chemical ionization atmospheric-pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a kinetic model. We found molar yields in the range of 3.5–6.5 % for HOM formation and 22–32 % for the formation of stabilized Criegee intermediates by fitting our model to the measured sulfuric acid concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulfuric acid formation was faster than simulated. In those experiments the simulated and measured concentrations met when the concentration reached a plateau but the plateau was reached 20–50 min later in the simulations. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help us to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

Sulfuric acid, amines and oxidized organics have been found to be important compounds in the nucleation and initial growth of atmospheric particles. Because of the challenges involved in determining the chemical composition of objects with very small mass, however, the properties of the freshly nucleated particles and the detailed pathways of their formation processes are still not clear. In this study, we focus on a challenging size range, i.e. particles that have grown to diameters of 10 and 15 nm following nucleation, and measure their water uptake. Water uptake constrains their chemical composition. We use a nanometer-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) at subsaturated conditions (ca. 90 % relative humidity at 293 K) to measure the hygroscopicity of particles during the seventh Cosmics Leaving OUtdoor Droplets (CLOUD7) experiments performed at CERN in 2012. In CLOUD7, the hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid-dimethylamine, and sulfuric acid-organics derived from α-pinene oxidation. The hygroscopicity parameter κ decreased with increasing particle size indicating decreasing acidity of particles. No clear effect of the sulfuric acid monomer concentrations on the hygroscopicities of 10 nm particles produced from sulfuric acid and dimethylamine was observed, whereas the hygroscopicity of 15 nm particles sharply decreased with decreasing sulfuric acid monomer concentrations. In particular, when the concentrations of sulfuric acid was 5.1 × 106 molecules cm−3 in the gas phase, and the dimethylamine mixing ratio was 11.8 ppt, the measured κ of 15 nm particles was 0.31 ± 0.01 close to the value reported for dimethylamine sulfate (DMAS) (κDMAS ~ 0.28). Furthermore, the difference in κ between sulfuric acid and sulfuric acid-dimethylamine experiments increased with increasing particle size. The κ values of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine. This suggests that the organics produced from α-pinene ozonolysis play a significant role in particle growth already at 10 nm sizes.

Article, Sulfuric acid, amines and oxidized organics have been found to be important compounds in the nucleation and initial growth of atmospheric particles. Because of the challenges involved in determining the chemical composition of objects with very small mass, however, the properties of the freshly nucleated particles and the detailed pathways of their formation processes are still not clear. In this study, we focus on a challenging size range, i.e., particles that have grown to diameters of 10 and 15 nm following nucleation, and measure their water uptake. Water uptake is useful information for indirectly obtaining chemical composition of aerosol particles. We use a nanometer-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) at subsaturated conditions (ca. 90 % relative humidity at 293 K) to measure the hygroscopicity of particles during the seventh Cosmics Leaving OUtdoor Droplets (CLOUD7) campaign performed at CERN in 2012. In CLOUD7, the hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid–dimethylamine, and sulfuric acid–organics derived from α-pinene oxidation. The hygroscopicity parameter κ decreased with increasing particle size, indicating decreasing acidity of particles. No clear effect of the sulfuric acid concentration on the hygroscopicity of 10 nm particles produced from sulfuric acid and dimethylamine was observed, whereas the hygroscopicity of 15 nm particles sharply decreased with decreasing sulfuric acid concentrations. In particular, when the concentration of sulfuric acid was 5.1 × 106 molecules cm−3 in the gas phase, and the dimethylamine mixing ratio was 11.8 ppt, the measured κ of 15 nm particles was 0.31 ± 0.01: close to the value reported for dimethylaminium sulfate (DMAS) (κDMAS ∼ 0.28). Furthermore, the difference in κ between sulfuric acid and sulfuric acid–imethylamine experiments increased with increasing particle size. The κ values of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine. This suggests that the organics produced from α-pinene ozonolysis play a significant role in particle growth even at 10 nm sizes., published version, peerReviewed

Measuring sub-3 nm particles outside of controlled laboratory conditions is a challenging task, as many of the instruments are operated at their limits and are subjected to changing ambient conditions. In this study, we advance the current understanding on the operation of Airmodus A11 nano Condensation Nucleus Counter (nCNC), which consists of a A10 Particle Size Magnifier (PSM) and A20 condensation particle counter (CPC). We explore the effect of the inlet line pressure on the measured particle concentration. We identify two different regions inside the instrument where supersaturation of working fluid can take place. We show the possibility of varying the cut-off of the instrument from 1 to 6 nm, a wider size range than the one usually covered by the PSM. We also present a new inlet system, which allows automated measurements of the background, minimizes the diffusion losses in the sampling line and is equipped with an electrostatic filter to remove ions. Finally, our view of the guidelines for optimal use of the Airmodus nCNC are provided.

Reliable and reproducible measurements of atmospheric aerosol particle number size distributions below 10 nm require optimized classification instruments with high particle transmission efficiency. Almost all DMAs have an unfavorable potential gradient at the outlet (e.g. long column, Vienna type) or at the inlet (nano-radial DMA). This feature prevents them from achieving a good transmission efficiency for the smallest nanoparticles. We developed a new high transmission inlet for the Caltech nano-radial DMA (nRDMA) that increases the transmission efficiency to 12 % for ions as small as 1.3 nm in mobility equivalent diameter (corresponding to 1.2 × 10−4 m2 V−1 s−1 in electrical mobility). We successfully deployed the nRDMA, equipped with the new inlet, in chamber measurements, using a Particle Size Magnifier (PSM) and a booster Condensation Particle Counter (CPC) as a counter. With this setup, we were able to measure size distributions of ions between 1.3 and 6 nm, corresponding to a mobility range from 1.2 × 10−4 to 5.8 × 10−6 m2 V−1 s−1. The system was modeled, tested in the laboratory and used to measure negative ions at ambient concentrations in the CLOUD 7 measurement campaign at CERN. We achieved a higher size resolution than techniques currently used in field measurements, and maintained a good transmission efficiency at moderate inlet and sheath air flows (2.5 and 30 LPM, respectively). In this paper, by measuring size distribution at high size resolution down to 1.3 nm, we extend the limit of the current technology. The current setup is limited to ion measurements. However, we envision that future research focused on the charging mechanisms could extend the technique to measure neutral aerosol particles as well, so that it will be possible to measure size distributions of ambient aerosols from 1 nm to 1 μm.

We present the results of laboratory measurements of the ion-ion recombination coefficient at different temperatures, relative humidities and concentrations of ozone and sulfur dioxide. The experiments were carried out using the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at CERN, the walls of which are made of conductive material, making it possible to measure small ions. We produced ions in the chamber using a 3.5 GeV c−1 beam of positively-charged pions (π+) from the CERN Proton Synchrotron (PS) and with galactic cosmic rays, when the PS was switched off. The range of the ion production rate varied from 2 to 100 cm−3s−1, covering the typical range of ionization throughout the troposphere. The temperature ranged from −55 to 20 °C, the relative humidity from 0 to 70%, the SO2 concentration from 0 to 40 ppb, and the ozone concentration from 200 to 700 ppb. At 20 °C and 40% RH, the retrieved ion-ion recombination coefficient was (2.3 ± 0.7) × 10−6cm3s−1. We observed no dependency of the ion-ion recombination coefficient on ozone concentration and a weak variation with sulfur dioxide concentration. However, we found a strong dependency of the ion-ion recombination coefficient on temperature. We compared our results with three different models and found an overall agreement for temperatures above 0 °C, but a disagreement at lower temperatures. We observed a strong dependency of the recombination coefficient on relative humidity, which has not been reported previously.

Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Jülich Plant-Atmosphere Simulation Chamber with instrumentation for the detection of sulphuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulphuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOC). We present direct laboratory observations of nanoparticle formation from sulphuric acid and realistic BVOC precursor vapor mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulphuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulphuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.

The metallurgical industry in the Kola Peninsula, north-west Russia, form, after Norilsk, Siberia, the second largest source of air pollution in the Arctic and subarctic domain. Sulfur dioxide (SO2) emissions from the ore smelters are transported to wide areas, including Finnish Lapland. We performed investigations on concentrations of SO2, aerosol precursor vapours, aerosol and ion cluster size distributions together with chemical composition measurements of freshly formed clusters at the SMEAR I station in Finnish Lapland relatively close (∼ 300 km) to the Kola Peninsula industrial sites during the winter 2019–2020. We show that highly concentrated SO2 from smelter emissions is converted to sulfuric acid (H2SO4) in sufficient concentrations to drive new particle formation hundreds of kilometres downwind from the emission sources, even at very low solar radiation intensities. Observed new particle formation is primarily initiated by H2SO4–ammonia (negative-)ion-induced nucleation. Particle growth to cloud condensation nuclei (CCN) sizes was concluded to result from sulfuric acid condensation. However, air mass advection had a large role in modifying aerosol size distributions, and other growth mechanisms and condensation of other compounds cannot be fully excluded. Our results demonstrate the dominance of SO2 emissions in controlling wintertime aerosol and CCN concentrations in the subarctic region with a heavily polluting industry.

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles ( nm) from sulfuric acid remain poorly measured. Therefore, the effect of stabilizing bases, the contribution of ions and the impact of attractive forces on molecular collisions are under debate. Here, we present precise growth rate measurements of uncharged sulfuric acid particles from 1.8 to 10 nm, performed under atmospheric conditions in the CERN (European Organization for Nuclear Research) CLOUD chamber. Our results show that the evaporation of sulfuric acid particles above 2 nm is negligible, and growth proceeds kinetically even at low ammonia concentrations. The experimental growth rates exceed the hard-sphere kinetic limit for the condensation of sulfuric acid. We demonstrate that this results from van der Waals forces between the vapour molecules and particles and disentangle it from charge–dipole interactions. The magnitude of the enhancement depends on the assumed particle hydration and collision kinetics but is increasingly important at smaller sizes, resulting in a steep rise in the observed growth rates with decreasing size. Including the experimental results in a global model, we find that the enhanced growth rate of sulfuric acid particles increases the predicted particle number concentrations in the upper free troposphere by more than 50 %.