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A list of authors and their affiliations appears at the end of the paper New-particle formation is a major contributor to urban smog, but how it occurs in cities is often puzzling. 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.
The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nano-particle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e. in conditions where neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.2 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.2 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.2 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.
A new method for size-resolved chemical analysis of nucleation mode aerosol particles (size range from ∼10 to ∼30 nm) is presented. The Thermal Desorption Differential Mobility Analyzer (TD-DMA) uses an online, discontinuous principle. The particles are charged, a specific size is selected by differential mobility analysis and they are collected on a filament by electrostatic precipitation. Subsequently, the sampled mass is evaporated in a clean carrier gas and analyzed by a chemical ionization mass spectrometer. Gas-phase measurements are performed with the same mass spectrometer during the sampling of particles. The characterization shows reproducible results, with a particle size resolution of 1.19 and the transmission efficiency for 15 nm particles being slightly above 50 %. The signal from the evaporation of a test substance can be detected starting from 0.01 ng and shows a linear response in the mass spectrometer. Instrument operation in the range of pg m−3 is demonstrated by an example measurement of 15 nm particles produced by nucleation from dimethylamine, sulfuric acid and water.
A new method for size resolved chemical analysis of nucleation mode aerosol particles (size range from ~10 to ~30 nm) is presented. The Thermal Desorption Differential Mobility Analyzer (TD-DMA) uses an online, discontinuous principle. The particles are charged, a specific size is selected by differential mobility analysis and they are collected on a filament by electrostatic precipitation. Subsequently, the sampled mass is evaporated in a clean carrier gas and analyzed by a chemical ionization mass spectrometer. Gas phase measurements are performed with the same mass spectrometer during the sampling of particles. The characterization shows reproducible results, with a particle size resolution of 1.19 and the transmission efficiency for 15 nm particles being slightly above 50 %. The signal from the evaporation of a test substance can be detected starting from 0.01 ng and shows a linear response in the mass spectrometer. Instrument operation in the range of pg/m3 is demonstrated by an example measurement of 15 nm particles produced by nucleation from dimethylamine, sulfuric acid and water.
We present a study characterizing aerosol particles resulting from a skyscraper blasting. High mass concentrations with a maximum of 844.9 μg m-3 were present for a short time period of approximately 15 minutes. They result in a day mean of 32.6 μg m-3 compared to a 27.6 μg m-3 background not exceeding the 50 μg m-3 EU maximum permissive value. The increase in particle number concentration was less pronounced with a maximum concentration of 6.9 ⋅ 104 cm-3 compared to the local background value of 1.8 ⋅ 104 cm-3. The size-resolved number concentration shows a single mode of ultrafine particles at approximately 93 nm. The spatial distribution of deposited dust was investigated with Bergerhoff glass collection vessels, showing a decrease with distance. In the deposited dust samples the concentrations of twelve metals was determined, non of them exceeded the regional background concentrations significantly. The chemical composition of individual particles emitted by the demolition was studied by Scanning Electron Microscopy. They were mainly concrete and steel particles, with 60% calcium carbonates, 19% calcium sulfates, 19% silicates and 2% steel. In energy-dispersive X-Ray Spectroscopy, no fibers like asbestos were observed. Using a broad spectrum of instruments and methods, we obtain comprehensive characterization of the particles emitted by the demolition.
Atmospheric nanoaerosols have extensive effects on the Earth’s climate and human health. This cumulative work focuses on the development and characterization of instrumentation for measuring various parameters of atmospheric nanoaerosols, and its use to understand new particle formation from organic precursors. The principal research question is, how the chemical composition of nanoaerosol particles can be measured and how atmospheric chemistry influences aerosol processes, especially new particle formation and growth. Therefore, nanoaerosols are investigated under various aspects. More specifically, an instrument is developed to analyze nanoparticles, and field as well as chamber studies are conducted.
The main project is the instrument development of the Thermal Desorption Differential Mobility Analyzer (TD-DMA, project 1, Wagner et al. (2018)). This instrument analyzes the chemical composition of small aerosol particles. By characterization and testing in chamber experiments, it is proven to be suitable for the analysis of freshly nucleated particles.
The second project (Wagner et al. (2017)) applies a broad spectrum of aerosol measurement instruments for the characterization of aerosol particles produced by a skyscraper blasting. A comprehensive picture of the particle population emitted by the demolition is obtained.
Project 3 (K¨urten et al. (2016)) is also an ambient aerosol measurement, focusing of new particle formation in a rural area in central Germany, and the ability of a negative nitrate CI-APi-TOF to detect various substances in atmosphere. Project 4 (Heinritzi et al. (2016)) is a characterization of the negative nitrate CI-APi-TOF used in projects 1, 3, 5, 6, 7 and 8. The following projects focus on understanding new particle formation from atmospherically abundant organic precursors. Key instruments comprise the negative nitrate CI-APiTOF for gas-phase measurements of the nucleating species, and various sizing and counting instruments for quantifying the particle formation and growth. Project 5 (Kirkby et al. (2016)) shows that biogenic organic compounds formed from alpha-pinene can nucleate on their own without the influence of e.g. sulfuric acid. Project 6 (Tr¨ostl et al. (2016)) describe the subsequent growth of these particles. Project 7 (Stolzenburg et al. (2018)) covers the temperature dependence of this growth and in project 8 (Heinritzi et al. (2018)), the suppressing influence of isoprene on the new particle formation is assessed.
About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday1. Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres2,3. In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles4, thereby failing to form new cloud condensation nuclei that are typically 50 to 100 nanometres across. Sulfuric acid vapour is often involved in nucleation but is too scarce to explain most subsequent growth5,6, leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer7,8,9,10. Although recent studies11,12,13 predict that low-volatility organic vapours contribute during initial growth, direct evidence has been lacking. The accelerating growth may result from increased photolytic production of condensable organic species in the afternoon2, and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Köhler theory)2,14, has so far remained ambiguous. Here we present experiments performed in a large chamber under atmospheric conditions that investigate the role of organic vapours in the initial growth of nucleated organic particles in the absence of inorganic acids and bases such as sulfuric acid or ammonia and amines, respectively. Using data from the same set of experiments, it has been shown15 that organic vapours alone can drive nucleation. We focus on the growth of nucleated particles and find that the organic vapours that drive initial growth have extremely low volatilities (saturation concentration less than 10−4.5 micrograms per cubic metre). As the particles increase in size and the Kelvin barrier falls, subsequent growth is primarily due to more abundant organic vapours of slightly higher volatility (saturation concentrations of 10−4.5 to 10−0.5 micrograms per cubic metre). We present a particle growth model that quantitatively reproduces our measurements. Furthermore, we implement a parameterization of the first steps of growth in a global aerosol model and find that concentrations of atmospheric cloud concentration nuclei can change substantially in response, that is, by up to 50 per cent in comparison with previously assumed growth rate parameterizations.
Nucleation and growth of aerosol particles from atmospheric vapors constitutes a major source of global cloud condensation nuclei (CCN). The fraction of newly formed particles that reaches CCN sizes is highly sensitive to particle growth rates, especially for particle sizes <10 nm, where coagulation losses to larger aerosol particles are greatest. Recent results show that some oxidation products from biogenic volatile organic compounds are major contributors to particle formation and initial growth. However, whether oxidized organics contribute to particle growth over the broad span of tropospheric temperatures remains an open question, and quantitative mass balance for organic growth has yet to be demonstrated at any temperature. Here, in experiments performed under atmospheric conditions in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN), we show that rapid growth of organic particles occurs over the range from −25 ∘C to 25 ∘C. The lower extent of autoxidation at reduced temperatures is compensated by the decreased volatility of all oxidized molecules. This is confirmed by particle-phase composition measurements, showing enhanced uptake of relatively less oxygenated products at cold temperatures. We can reproduce the measured growth rates using an aerosol growth model based entirely on the experimentally measured gas-phase spectra of oxidized organic molecules obtained from two complementary mass spectrometers. We show that the growth rates are sensitive to particle curvature, explaining widespread atmospheric observations that particle growth rates increase in the single-digit-nanometer size range. Our results demonstrate that organic vapors can contribute to particle growth over a wide range of tropospheric temperatures from molecular cluster sizes onward.
Cloud microphysical processes involving the ice phase in tropospheric clouds are among the major uncertainties in cloud formation, weather, and general circulation models. The detection of aerosol particles, liquid droplets, and ice crystals, especially in the small cloud particle-size range below 50 μm, remains challenging in mixed phase, often unstable environments. The Cloud Aerosol Spectrometer with Polarization (CASPOL) is an airborne instrument that has the ability to detect such small cloud particles and measure the variability in polarization state of their backscattered light. Here we operate the versatile Cosmics Leaving OUtdoor Droplets (CLOUD) chamber facility at the European Organization for Nuclear Research (CERN) to produce controlled mixed phase and other clouds by adiabatic expansions in an ultraclean environment, and use the CASPOL to discriminate between different aerosols, water, and ice particles. In this paper, optical property measurements of mixed-phase clouds and viscous secondary organic aerosol (SOA) are presented. We report observations of significant liquid–viscous SOA particle polarization transitions under dry conditions using CASPOL. Cluster analysis techniques were subsequently used to classify different types of particles according to their polarization ratios during phase transition. A classification map is presented for water droplets, organic aerosol (e.g., SOA and oxalic acid), crystalline substances such as ammonium sulfate, and volcanic ash. Finally, we discuss the benefits and limitations of this classification approach for atmospherically relevant concentrations and mixtures with respect to the CLOUD 8–9 campaigns and its potential contribution to tropical troposphere layer analysis.
Cloud microphysical processes involving the ice phase in tropospheric clouds are among the major uncertainties in cloud formation, weather and General Circulation Models (GCMs). The simultaneous detection of aerosol particles, liquid droplets, and ice crystals, especially in the small cloud-particle size range below 50 µm, remains challenging in mixed phase, often unstable ice-water phase environments. The Cloud Aerosol Spectrometer with Polarisation (CASPOL) is an airborne instrument that has the ability to detect such small cloud particles and measure their effects on the backscatter polarisation state. Here we operate the versatile Cosmics-Leaving- OUtdoor-Droplets (CLOUD) chamber facility at the European Organisation for Nuclear Research (CERN) to produce controlled mixed phase and other clouds by adiabatic expansions in an ultraclean environment, and use the CASPOL to discriminate between different aerosols, water and ice particles. In this paper, optical property measurements of mixed phase clouds and viscous Secondary Organic Aerosol (SOA) are presented. We report observations of significant liquid – viscous SOA particle polarisation transitions under dry conditions using CASPOL. Cluster analysis techniques were subsequently used to classify different types of particles according to their polarisation ratios during phase transition. A classification map is presented for water droplets, organic aerosol (e.g., SOA and oxalic acid), crystalline substances such as ammonium sulphate, and volcanic ash. Finally, we discuss the benefits and limitations of this classi- fication approach for atmospherically relevant concentration and mixtures with respect to the CLOUD 8–9 campaigns and its potential contribution to Tropical Troposphere Layer (TTL) analysis.