Faster than expected: Iodine species are one of only a handful of atmospheric vapors known to make new aerosol particles, which play a central role in controlling the radiative forcing of climate. He et al. report experimental evidence from the CERN Cosmics Leaving Outdoor Droplets, or CLOUD, chamber demonstrating that iodic acid and iodous acid rapidly form new particles and can compete with sulfuric acid in pristine regions. Science , this issue p. 589

Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to −50 ^∘C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J_1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25 ^∘C to 0.7 % at −50 ^∘C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at −50 ^∘C compared with 25 ^∘C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

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 (<10 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 %.

Knowledge about mass discrimination effects in a chemical ionization mass spectrometer (CIMS) is crucial for quantifying, e.g., the recently discovered extremely low volatile organic compounds (ELVOCs) and other compounds for which no calibration standard exists so far. Here, we present a simple way of estimating mass discrimination effects of a nitrate-based chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer. Characterization of the mass discrimination is achieved by adding different perfluorinated acids to the mass spectrometer in amounts sufficient to deplete the primary ions significantly. The relative transmission efficiency can then be determined by comparing the decrease of signals from the primary ions and the increase of signals from the perfluorinated acids at higher masses. This method is in use already for PTR-MS; however, its application to a CI-APi-TOF brings additional difficulties, namely clustering and fragmentation of the measured compounds, which can be treated with statistical analysis of the measured data, leading to self-consistent results. We also compare this method to a transmission estimation obtained with a setup using an electrospray ion source, a high-resolution differential mobility analyzer and an electrometer, which estimates the transmission of the instrument without the CI source. Both methods give different transmission curves, indicating non-negligible mass discrimination effects of the CI source. The absolute transmission of the instrument without the CI source was estimated with the HR-DMA method to plateau between the m∕z range of 127 and 568 Th at around 1.5 %; however, for the CI source included, the depletion method showed a steady increase in relative transmission efficiency from the m∕z range of the primary ion (mainly at 62 Th) to around 550 Th by a factor of around 5. The main advantages of the depletion method are that the instrument is used in the same operation mode as during standard measurements and no knowledge of the absolute amount of the measured substance is necessary, which results in a simple setup.

Nucleation of atmospheric vapours produces more than half of global cloud condensation nuclei and so has an important influence on climate. Recent studies show that monoterpene (C₁₀H₁₆) oxidation yields highly oxygenated products that can nucleate with or without sulfuric acid. Monoterpenes are emitted mainly by trees, frequently together with isoprene (C₅H₈), which has the highest global emission of all organic vapours. Previous studies have shown that isoprene suppresses new-particle formation from monoterpenes, but the cause of this suppression is under debate. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we show that isoprene reduces the yield of highly oxygenated dimers with 19 or 20 carbon atoms – which drive particle nucleation and early growth – while increasing the production of dimers with 14 or 15 carbon atoms. The dimers (termed C₂₀ and C₁₅, respectively) are produced by termination reactions between pairs of peroxy radicals (RO₂⚫ ) arising from monoterpenes or isoprene. Compared with pure monoterpene conditions, isoprene reduces nucleation rates at 1.7 nm (depending on the isoprene ∕ monoterpene ratio) and approximately halves particle growth rates between 1.3 and 3.2 nm. However, above 3.2 nm, C₁₅ dimers contribute to secondary organic aerosol, and the growth rates are unaffected by isoprene. We further show that increased hydroxyl radical (OH⚫ ) reduces particle formation in our chemical system rather than enhances it as previously proposed, since it increases isoprene-derived RO₂⚫ radicals that reduce C₂₀ formation. RO₂⚫ termination emerges as the critical step that determines the highly oxygenated organic molecule (HOM) distribution and the corresponding nucleation capability. Species that reduce the C₂₀ yield, such as NO, HO₂ and as we show isoprene, can thus effectively reduce biogenic nucleation and early growth. Therefore the formation rate of organic aerosol in a particular region of the atmosphere under study will vary according to the precise ambient conditions.

The exact mechanisms for new particle formation (NPF) under different boundary layer conditions are not known yet. One important question is whether amines and sulfuric acid lead to efficient NPF in the atmosphere. Furthermore, it is not clear to what extent highly oxidized organic molecules (HOMs) are involved in NPF. We conducted field measurements at a rural site in central Germany in the proximity of three larger dairy farms to investigate whether there is a connection between NPF and the presence of amines and/or ammonia due to the local emissions from the farms. Comprehensive measurements using a nitrate chemical ionization–atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer, a proton-transfer-reaction mass spectrometer (PTR-MS), particle counters and differential mobility analyzers (DMAs), as well as measurements of trace gases and meteorological parameters, were performed. We demonstrate here that the nitrate CI-APi-TOF is suitable for sensitive measurements of sulfuric acid, amines, a nitrosamine, ammonia, iodic acid and HOMs. NPF was found to correlate with sulfuric acid, while an anti-correlation with RH, amines and ammonia is observed. The anti-correlation between NPF and amines could be due to the efficient uptake of these compounds by nucleating clusters and small particles. Much higher HOM dimer (C₁₉/C₂₀ compounds) concentrations during the night than during the day indicate that these HOMs do not efficiently self-nucleate as no nighttime NPF is observed. Observed iodic acid probably originates from an iodine-containing reservoir substance, but the iodine signals are very likely too low to have a significant effect on NPF.