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Learning more about how pollutants enter and damage the body would reduce disease and deaths, say Jos Lelieveld and Ulrich Pöschl. Learning more about how pollutants enter and damage the body would reduce disease and deaths, say Jos Lelieveld and Ulrich Pöschl.

The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.

Many cities in India experience severe deterioration of air quality in winter. Particulate matter is a key atmospheric pollutant that impacts millions of people. In particular, the high mass concentration of particulate matter reduces visibility, which has severely damaged the economy and endangered human lives. But the underlying chemical mechanisms and physical processes responsible for initiating haze and fog formation remain poorly understood. Here we present the measurement results of chemical composition of particulate matter in Delhi and Chennai. We find persistently high chloride in Delhi and episodically high chloride in Chennai. These measurements, combined with thermodynamic modelling, suggest that in the presence of excess ammonia in Delhi, high local emission of hydrochloric acid partitions into aerosol water. The highly water-absorbing and soluble chloride in the aqueous phase substantially enhances aerosol water uptake through co-condensation, which sustains particle growth, leading to haze and fog formation. We therefore suggest that the high local concentration of gas-phase hydrochloric acid, possibly emitted from plastic-contained waste burning and industry, causes some 50% of the reduced visibility. Our work implies that identifying and regulating gaseous hydrochloric acid emissions could be critical to improve visibility and human health in India. Half of the reduced visibility due to haze formation in cities in India is attributed to local emission of gas-phase hydrochloric acid from waste-burning and industry, according to measurements of particulate matter and thermodynamic modelling.

Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate.

Many terrestrial surfaces are covered by photoautotrophic communities, which are capable of synthesizing their own food from inorganic substances using sunlight. According to an analysis of previously published data, these communities account for nearly half of the biological nitrogen fixation on land. Many terrestrial surfaces, including soils, rocks and plants, are covered by photoautotrophic communities, capable of synthesizing their own food from inorganic substances using sunlight as an energy source 1 , 2 . These communities, known as cryptogamic covers, comprise variable proportions of cyanobacteria, algae, fungi, lichens and bryophytes, and are able to fix carbon dioxide and nitrogen from the atmosphere 3 . However, their influence on global and regional biogeochemical cycling of carbon and nitrogen has not yet been assessed. Here, we analyse previously published data on the spatial coverage of cryptogamic communities, and the associated fluxes of carbon and nitrogen, in different types of ecosystem across the globe. We estimate that globally, cryptogamic covers take up around 3.9 Pg carbon per year, corresponding to around 7% of net primary production by terrestrial vegetation. We derive a nitrogen uptake by cryptogamic covers of around 49 Tg per year, suggesting that cryptogamic covers account for nearly half of the biological nitrogen fixation on land. We suggest that nitrogen fixation by cryptogamic covers may be crucial for carbon sequestration by plants.

Secondary organic aerosols (SOA) are a large source of uncertainty in our current understanding of climate change and air pollution. The phase state of SOA is important for quantifying their effects on climate and air quality, but its global distribution is poorly characterized. We developed a method to estimate glass transition temperatures based on the molar mass and molecular O:C ratio of SOA components, and we used the global chemistry climate model EMAC with the organic aerosol module ORACLE to predict the phase state of atmospheric SOA. For the planetary boundary layer, global simulations indicate that SOA are mostly liquid in tropical and polar air with high relative humidity, semi-solid in the mid-latitudes and solid over dry lands. We find that in the middle and upper troposphere SOA should be mostly in a glassy solid phase state. Thus, slow diffusion of water, oxidants and organic molecules could kinetically limit gas–particle interactions of SOA in the free and upper troposphere, promote ice nucleation and facilitate long-range transport of reactive and toxic organic pollutants embedded in SOA. Secondary organic aerosols (SOA) are important for climate and aerosol quality, but the phase state is unclear. Here, the authors show that SOA is liquid in tropical and polar air, semi-solid in the mid-latitudes, solid over dry lands and in a glassy solid phase state in the middle and upper troposphere.

Fine particulate matter plays a central role in the adverse health effects of air pollution. Inhalation and deposition of aerosol particles in the respiratory tract can lead to the release of reactive oxygen species (ROS), which may cause oxidative stress. In this study, we have detected and quantified a wide range of particle-associated radicals using electron paramagnetic resonance (EPR) spectroscopy. Ambient particle samples were collected using a cascade impactor at a semi-urban site in central Europe, Mainz, Germany, in May–June 2015. Concentrations of environmentally persistent free radicals (EPFR), most likely semiquinone radicals, were found to be in the range of (1–7)  × 1011 spins µg−1 for particles in the accumulation mode, whereas coarse particles with a diameter larger than 1 µm did not contain substantial amounts of EPFR. Using a spin trapping technique followed by deconvolution of EPR spectra, we have also characterized and quantified ROS, including OH, superoxide (O2−) and carbon- and oxygen-centered organic radicals, which were formed upon extraction of the particle samples in water. Total ROS amounts of (0.1–3)  × 1011 spins µg−1 were released by submicron particle samples and the relative contributions of OH, O2−, C-centered and O-centered organic radicals were ∼  11–31, ∼  2–8, ∼  41–72 and ∼  0–25 %, respectively, depending on particle sizes. OH was the dominant species for coarse particles. Based on comparisons of the EPR spectra of ambient particulate matter with those of mixtures of organic hydroperoxides, quinones and iron ions followed by chemical analysis using liquid chromatography mass spectrometry (LC-MS), we suggest that the particle-associated ROS were formed by decomposition of organic hydroperoxides interacting with transition metal ions and quinones contained in atmospheric humic-like substances (HULIS).

Reactive nitrogen species have a strong influence on atmospheric chemistry and climate, tightly coupling the Earth’s nitrogen cycle with microbial activity in the biosphere. Their sources, however, are not well constrained, especially in dryland regions accounting for a major fraction of the global land surface. Here, we show that biological soil crusts (biocrusts) are emitters of nitric oxide (NO) and nitrous acid (HONO). Largest fluxes are obtained by dark cyanobacteria-dominated biocrusts, being ∼20 times higher than those of neighboring uncrusted soils. Based on laboratory, field, and satellite measurement data, we obtain a best estimate of ∼1.7 Tg per year for the global emission of reactive nitrogen from biocrusts (1.1 Tg a⁻¹ of NO-N and 0.6 Tg a⁻¹ of HONO-N), corresponding to ∼20% of global nitrogen oxide emissions from soils under natural vegetation. On continental scales, emissions are highest in Africa and South America and lowest in Europe. Our results suggest that dryland emissions of reactive nitrogen are largely driven by biocrusts rather than the underlying soil. They help to explain enigmatic discrepancies between measurement and modeling approaches of global reactive nitrogen emissions. As the emissions of biocrusts strongly depend on precipitation events, climate change affecting the distribution and frequency of precipitation may have a strong impact on terrestrial emissions of reactive nitrogen and related climate feedback effects. Because biocrusts also account for a large fraction of global terrestrial biological nitrogen fixation, their impacts should be further quantified and included in regional and global models of air chemistry, biogeochemistry, and climate.

Phase transitions of nanoparticles are of fundamental importance in atmospheric sciences, but current understanding is insufficient to explain observations at the nano-scale. In particular, discrepancies exist between observations and model predictions of deliquescence and efflorescence transitions and the hygroscopic growth of salt nanoparticles. Here we show that these discrepancies can be resolved by consideration of particle size effects with consistent thermodynamic data. We present a new method for the determination of water and solute activities and interfacial energies in highly supersaturated aqueous solution droplets (Differential Köhler Analysis). Our analysis reveals that particle size can strongly alter the characteristic concentration of phase separation in mixed systems, resembling the influence of temperature. Owing to similar effects, atmospheric secondary organic aerosol particles at room temperature are expected to be always liquid at diameters below ~20 nm. We thus propose and demonstrate that particle size should be included as an additional dimension in the equilibrium phase diagram of aerosol nanoparticles. Although phase transitions are fundamental for understanding aerosol particles, current models are insufficient to explain observations at the nanoscale. Here, the authors present a method for investigating droplets, suggesting particle size is a key determinant in the phase diagram of nanoparticles.

We found that ambient and laboratory-generated secondary organic aerosols (SOA) form substantial amounts of OH radicals upon interaction with liquid water, which can be explained by the decomposition of organic hydroperoxides. The molar OH yield from SOA formed by ozonolysis of terpenes (α-pinene, β-pinene, limonene) is  ∼  0.1 % upon extraction with pure water and increases to  ∼  1.5 % in the presence of Fe2+ ions due to Fenton-like reactions. Upon extraction of SOA samples from OH photooxidation of isoprene, we also detected OH yields of around  ∼  0.1 %, which increases upon addition of Fe2+. Our findings imply that the chemical reactivity and aging of SOA particles is strongly enhanced upon interaction with water and iron. In cloud droplets under dark conditions, SOA decomposition can compete with the classical H2O2 Fenton reaction as the source of OH radicals. Also in the human respiratory tract, the inhalation and deposition of SOA particles may lead to a substantial release of OH radicals, which may contribute to oxidative stress and play an important role in the adverse health effects of atmospheric aerosols.