A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog^1,2, but how it occurs in cities is often puzzling³. If the growth rates of urban particles are similar to those found in cleaner environments (1–10 nanometres per hour), then existing understanding suggests that new urban particles should be rapidly scavenged by the high concentration of pre-existing particles. Here we show, through experiments performed under atmospheric conditions in the CLOUD chamber at CERN, that below about +5 degrees Celsius, nitric acid and ammonia vapours can condense onto freshly nucleated particles as small as a few nanometres in diameter. Moreover, when it is cold enough (below −15 degrees Celsius), nitric acid and ammonia can nucleate directly through an acid–base stabilization mechanism to form ammonium nitrate particles. Given that these vapours are often one thousand times more abundant than sulfuric acid, the resulting particle growth rates can be extremely high, reaching well above 100 nanometres per hour. However, these high growth rates require the gas-particle ammonium nitrate system to be out of equilibrium in order to sustain gas-phase supersaturations. In view of the strong temperature dependence that we measure for the gas-phase supersaturations, we expect such transient conditions to occur in inhomogeneous urban settings, especially in wintertime, driven by vertical mixing and by strong local sources such as traffic. Even though rapid growth from nitric acid and ammonia condensation may last for only a few minutes, it is nonetheless fast enough to shepherd freshly nucleated particles through the smallest size range where they are most vulnerable to scavenging loss, thus greatly increasing their survival probability. We also expect nitric acid and ammonia nucleation and rapid growth to be important in the relatively clean and cold upper free troposphere, where ammonia can be convected from the continental boundary layer and nitric acid is abundant from electrical storms^4,5.

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

Delhi, India, routinely experiences some of the world's highest urban particulate matter concentrations. We established the Delhi Aerosol Supersite study to provide long-term characterization of the ambient submicron aerosol composition in Delhi. Here we report on 1.25 years of highly time-resolved speciated submicron particulate matter (PM₁) data, including black carbon (BC) and nonrefractory PM₁ (NR-PM₁), which we combine to develop a composition-based estimate of PM₁ (“C-PM₁” = BC + NR-PM₁) concentrations. We observed marked seasonal and diurnal variability in the concentration and composition of PM₁ owing to the interactions of sources and atmospheric processes. Winter was the most polluted period of the year, with average C-PM₁ mass concentrations of ∼210 µg m⁻³. The monsoon was hot and rainy, consequently making it the least polluted (C-PM₁ ∼50 µg m⁻³) period. Organics constituted more than half of the C-PM₁ for all seasons and times of day. While ammonium, chloride, and nitrate each were ∼10 % of the C-PM₁ for the cooler months, BC and sulfate contributed ∼5 % each. For the warmer periods, the fractional contribution of BC and sulfate to C-PM₁ increased, and the chloride contribution decreased to less than 2 %. The seasonal and diurnal variation in absolute mass loadings were generally consistent with changes in ventilation coefficients, with higher concentrations for periods with unfavorable meteorology – low planetary boundary layer height and low wind speeds. However, the variation in C-PM₁ composition was influenced by temporally varying sources, photochemistry, and gas–particle partitioning. During cool periods when wind was from the northwest, episodic hourly averaged chloride concentrations reached 50–100 µg m⁻³, ranking among the highest chloride concentrations reported anywhere in the world. We estimated the contribution of primary emissions and secondary processes to Delhi's submicron aerosol. Secondary species contributed almost 50 %–70 % of Delhi's C-PM₁ mass for the winter and spring months and up to 60 %–80 % for the warmer summer and monsoon months. For the cooler months that had the highest C-PM₁ concentrations, the nighttime sources were skewed towards primary sources, while the daytime C-PM₁ was dominated by secondary species. Overall, these findings point to the important effects of both primary emissions and more regional atmospheric chemistry on influencing the extreme particle concentrations that impact the Delhi megacity region. Future air quality strategies considering Delhi's situation in both a regional and local context will be more effective than policies targeting only local, primary air pollutants.

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.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H ₂ SO ₄ ), stabilized by ammonia (NH ₃ ). However, in marine and polar regions, NH ₃ is generally low, and H ₂ SO ₄ is frequently found together with iodine oxoacids [HIO _x , i.e., iodic acid (HIO ₃ ) and iodous acid (HIO ₂ )]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H ₂ SO ₄ and HIO _x during atmospheric particle nucleation. We found that HIO _x greatly enhances H ₂ SO ₄ (-NH ₃ ) nucleation through two different interactions. First, HIO ₃ strongly binds with H ₂ SO ₄ in charged clusters so they drive particle nucleation synergistically. Second, HIO ₂ substitutes for NH ₃ , forming strongly bound H ₂ SO ₄ -HIO ₂ acid-base pairs in molecular clusters. Global observations imply that HIO _x is enhancing H ₂ SO ₄ (-NH ₃ ) nucleation rates 10- to 10,000-fold in marine and polar regions.

Chlorine-initiated oxidation of n-alkanes (C₈₋₁₂) under high-nitrogen oxide conditions was investigated. Observed secondary organic aerosol yields (0.16 to 1.65) are higher than those for OH-initiated oxidation of C₈₋₁₂ alkanes (0.04 to 0.35). A high-resolution time-of-flight chemical ionization mass spectrometer coupled to a Filter Inlet for Gases and AEROsols (FIGAERO–CIMS) was used to characterize the gas- and particle-phase molecular composition. Chlorinated organics were observed, which likely originated from chlorine addition to the double bond present on the heterogeneously produced dihydrofurans. A two-dimensional thermogram representation was developed to visualize the composition and relative volatility of organic aerosol components using unit-mass resolution data. Evidence of oligomer formation and thermal decomposition was observed. Aerosol yield and oligomer formation were suppressed under humid conditions (35 % to 67 % RH) relative to dry conditions (under 5 % RH). The temperature at peak desorption signal, T_max, a proxy for aerosol volatility, was shown to change with aerosol filter loading, which should be constrained when evaluating aerosol volatilities using the FIGAERO–CIMS. Results suggest that long-chain anthropogenic alkanes could contribute significantly to ambient aerosol loading over their atmospheric lifetime.