Search

Biomass burning emits ~34–41 Tg yr−1 of smoke aerosol to the atmosphere. Biomass burning aerosol directly influences the Earth’s climate by attenuation of solar and terrestrial radiation; however, its abundance and distribution on a global scale are poorly constrained, particularly after plumes dilute into the background remote troposphere and are subject to removal by clouds and precipitation. Here we report global-scale, airborne measurements of biomass burning aerosol in the remote troposphere. Measurements were taken during four series of seasonal flights over the Pacific and Atlantic Ocean basins, each with near pole-to-pole latitude coverage. We find that biomass burning particles in the remote troposphere are dilute but ubiquitous, accounting for one-quarter of the accumulation-mode aerosol number and one-fifth of the aerosol mass. Comparing our observations with a high-resolution global aerosol model, we find that the model overestimates biomass burning aerosol mass in the remote troposphere with a mean bias of >400%, largely due to insufficient wet removal by in-cloud precipitation. After updating the model’s aerosol removal scheme we find that, on a global scale, dilute smoke contributes as much as denser plumes to biomass burning’s scattering and absorption effects on the Earth’s radiation field. Aerosol particles produced by biomass burning are ubiquitous in the remote troposphere, according to global airborne measurements over remote ocean regions.

From 2016 to 2018 a DC-8 aircraft operated by the US National Aeronautics and Space Administration (NASA) made four series of flights, profiling the atmosphere from 180 m to ∼12 km above sea level (km a.s.l.) from the Arctic to the Antarctic over both the Pacific and Atlantic oceans. This program, the Atmospheric Tomography Mission (ATom), sought to sample the troposphere in a representative manner, making measurements of atmospheric composition in each season. This paper describes the aerosol microphysical measurements and derived quantities obtained during this mission. Dry size distributions from 2.7 nm to 4.8 µm in diameter were measured in situ at 1 Hz using a battery of instruments: 10 condensation particle counters with different nucleation diameters, two ultra-high-sensitivity aerosol size spectrometers (UHSASs), one of which measured particles surviving heating to 300 ∘C, and a laser aerosol spectrometer (LAS). The dry aerosol measurements were complemented by size distribution measurements from 0.5 to 930 µm diameter at near-ambient conditions using a cloud, aerosol, and precipitation spectrometer (CAPS) mounted under the wing of the DC-8. Dry aerosol number, surface area, and volume, and optical scattering and asymmetry parameters at several wavelengths from the near-UV to the near-IR ranges were calculated from the measured dry size distributions (2.7 nm to 4.8 µm). Dry aerosol mass was estimated by combining the size distribution data with particle density estimated from independent measurements of aerosol composition with a high-resolution aerosol mass spectrometer and a single-particle soot photometer. We describe the instrumentation and fully document the aircraft inlet and flow distribution system, the derivation of uncertainties, and the calculation of data products from combined size distributions. Comparisons between the instruments and direct measurements of some aerosol properties confirm that in-flight performance was consistent with calibrations and within stated uncertainties for the two deployments analyzed. The unique ATom dataset contains accurate, precise, high-resolution in situ measurements of dry aerosol size distributions, and integral parameters, and estimates and measurements of optical properties, for particles µm in diameter that can be used to evaluate aerosol abundance and processes in global models.

The inorganic fraction of fine particles affects numerous physicochemical processes in the atmosphere. However, there is large uncertainty in its burden and composition due to limited global measurements. Here, we present observations from eleven different aircraft campaigns from around the globe and investigate how aerosol pH and ammonium balance change from polluted to remote regions, such as over the oceans. Both parameters show increasing acidity with remoteness, at all altitudes, with pH decreasing from about 3 to about −1 and ammonium balance decreasing from almost 1 to nearly 0. We compare these observations against nine widely used chemical transport models and find that the simulations show more scatter (generally R2

The size of aerosol particles has fundamental effects on their chemistry and radiative effects. We explore those effects using aerosol size and composition data in the lowermost stratosphere along with calculations of light scattering. In the size range between about 0.1 and 1.0 µm diameter (accumulation mode), there are at least two modes of particles in the lowermost stratosphere. The larger mode consists mostly of particles produced in the stratosphere, and the smaller mode consists mostly of particles transported from the troposphere. The stratospheric mode is similar in the Northern and Southern Hemisphere, whereas the tropospheric mode is much more abundant in the Northern Hemisphere. The purity of sulfuric acid particles in the stratospheric mode shows that there is limited production of secondary organic aerosol in the stratosphere, especially in the Southern Hemisphere. Out of eight sets of flights sampling the lowermost stratosphere (four seasons and two hemispheres) there were three with large injections of specific materials: volcanic, biomass burning, or dust. The stratospheric and tropospheric modes have very different roles for radiative effects on climate and for heterogeneous chemistry. Because the larger particles are more efficient at scattering light, most of the radiative effect in the lowermost stratosphere is due to stratospheric particles. In contrast, the tropospheric particles can have more surface area, at least in the Northern Hemisphere. The surface area of tropospheric particles could have significant implications for heterogeneous chemistry because these particles, which are partially neutralized and contain organics, do not correspond to the substances used for laboratory studies of stratospheric heterogeneous chemistry. We then extend the analysis of size-dependent properties to particles injected into the stratosphere, either intentionally or from volcanoes. There is no single size that will simultaneously maximize the climate impact relative to the injected mass, infrared heating, potential for heterogeneous chemistry, and undesired changes in direct sunlight. In addition, light absorption in the far ultraviolet is identified as an issue requiring more study for both the existing and potentially modified stratosphere.

Brown carbon (BrC) is an organic aerosol material that preferentially absorbs light of shorter wavelengths. Global‐scale radiative impacts of BrC have been difficult to assess due to the lack of BrC observational data. To address this, aerosol filters were continuously collected with near pole‐to‐pole latitudinal coverage over the Pacific and Atlantic basins in three seasons as part of the Atmospheric Tomography Mission. BrC chromophores in filter extracts were measured. We find that globally, BrC was highly spatially heterogeneous, mostly detected in air masses that had been transported from regions of extensive biomass burning. We calculate the average direct radiative effect due to BrC absorption accounted for approximately 7% to 48% of the top of the atmosphere clear‐sky instantaneous forcing by all absorbing carbonaceous aerosols in the remote atmosphere, indicating that BrC from biomass burning is an important component of the global radiative balance., Key Points Globally, biomass burning is a large source of light‐absorbing carbonaceous aerosol that directly affect the planetary radiation balanceTransported over long distances, brown carbon is a significant component of these aerosols, but its contribution was highly variableBrown carbon contributed up to 48% of average clear‐sky instantaneous forcing by light absorption by carbonaceous aerosols

6 pags., 5 figs., Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate., Additional National Oceanic and Atmospheric Administration (NOAA) support for ATom was provided by NASA funding via Inter-Agency Transfer NNH15AB12l and by funding from the NOAA Climate Program Office and the NOAA Atmospheric Chemistry, Carbon Cycle, and Climate program. K.H.M. and H.G.K. acknowledge the financial support of the Independent Research Fund Denmark, the University of Copenhagen, and the Danish Ministry for Higher Education and Science’s Elite Research travel grant. J.L.J.’s group acknowledges NASA grants NHX15AH33A and 80NSSC19K0124. A.K. was supported by the Austrian Science Fund’s Erwin Schrodinger Fellowship. A.S.-L., Q.L., and C.A.C. are supported by the European Research Council (ERC) Executive Agency under the European Union’s Horizon 2020 Research and Innovation programme (Project ERC-2016-COG 726349 CLIMAHAL). The National Center for Atmospheric Research is sponsored by the National Science Foundation. E.A. and J.B. were funded in part by NASA Atmospheric Composition Program. T.H.B. and C.M.J. acknowledge support from the National Science Foundation Center for Aerosol Impacts on Chemistry of the Environment under grant CHE 1801971. B.W. and M.D. have received funding from the ERC under the European Union’s Horizon 2020 research and innovation framework program under grant 640458 (A-LIFE) and from the University of Vienna.

Earth's radiation budget is affected by new particle formation (NPF) and the growth of these nanometre-scale particles to larger sizes where they can directly scatter light or act as cloud condensation nuclei (CCN). Large uncertainties remain in the magnitude and spatiotemporal distribution of nucleation (less than 10 nm diameter) and Aitken (10–60 nm diameter) mode particles. Acquiring size-distribution measurements of these particles over large regions of the free troposphere is most easily accomplished with research aircraft. We report on the design and performance of an airborne instrument, the nucleation mode aerosol size spectrometer (NMASS), which provides size-selected aerosol concentration measurements that can be differenced to identify aerosol properties and processes or inverted to obtain a full size distribution between 3 and 60 nm. By maintaining constant downstream pressure the instrument operates reliably over a large range of ambient pressures and during rapid changes in altitude, making it ideal for aircraft measurements from the boundary layer to the stratosphere. We describe the modifications, operating principles, extensive calibrations, and laboratory and in-flight performance of two NMASS instruments operated in parallel as a 10-channel battery of condensation particle counters (CPCs) in the NASA Atmospheric Tomography Mission (ATom) to investigate NPF and growth to cloud-active sizes in the remote free troposphere. An inversion technique to obtain size distributions from the discrete concentrations of each NMASS channel is described and evaluated. Concentrations measured by the two NMASS instruments flying in parallel are self-consistent and also consistent with measurements made with an optical particle counter. Extensive laboratory calibrations with a range of particle sizes and compositions show repeatability of the response function of the instrument to within 5–8 % and no sensitivity in sizing performance to particle composition. Particle number, surface area, and volume concentrations from the data inversion are determined to better than 20 % for typical particle size distributions. The excellent performance of the NMASS systems provides a strong analytical foundation to explore NPF around the globe in the ATom dataset.

Atmospheric aerosol is a key component of the chemistry and climate of the Earth's atmosphere. Accurate measurement of the concentration of atmospheric particles as a function of their size is fundamental to investigations of particle microphysics, optical characteristics, and chemical processes. We describe the modification, calibration, and performance of two commercially available, Ultra-High Sensitivity Aerosol Spectrometers (UHSASs) as used on the NASA DC-8 aircraft during the Atmospheric Tomography Mission (ATom). To avoid sample flow issues related to pressure variations during aircraft altitude changes, we installed a laminar flow meter on each instrument to measure sample flow directly at the inlet as well as flow controllers to maintain constant volumetric sheath flows. In addition, we added a compact thermodenuder operating at 300 °C to the inlet line of one of the instruments. With these modifications, the instruments are capable of making accurate (ranging from 7 % for Dp Dp > 0.13 µm), precise ( 1000 to 225 hPa, while simultaneously providing information on particle volatility.We assessed the effect of uncertainty in the refractive index (n) of ambient particles that are sized by the UHSAS assuming the refractive index of ammonium sulfate (n = 1.52). For calibration particles with n between 1.44 and 1.58, the UHSAS diameter varies by +4/−10 % relative to ammonium sulfate. This diameter uncertainty associated with the range of refractive indices (i.e., particle composition) translates to aerosol surface area and volume uncertainties of +8.4/−17.8 and +12.4/−27.5 %, respectively. In addition to sizing uncertainty, low counting statistics can lead to uncertainties of 1000 cm−3.Examples of thermodenuded and non-thermodenuded aerosol number and volume size distributions as well as propagated uncertainties are shown for several cases encountered during the ATom project. Uncertainties in particle number concentration were limited by counting statistics, especially in the tropical upper troposphere where accumulation-mode concentrations were sometimes −3 (counting rates ∼ 5 Hz) at standard temperature and pressure.

The CLOUD (Cosmics Leaving OUtdoor Droplets) experiment at CERN (European Council for Nuclear Research) investigates the nucleation and growth of aerosol particles under atmospheric conditions and their activation into cloud droplets. A key feature of the CLOUD experiment is precise control of the experimental parameters. Temperature uniformity and stability in the chamber are important since many of the processes under study are sensitive to temperature and also to contaminants that can be released from the stainless steel walls by upward temperature fluctuations. The air enclosed within the 26 m3 CLOUD chamber is equipped with several arrays (strings) of high precision, fast-response thermometers to measure its temperature. Here we present a study of the air temperature uniformity inside the CLOUD chamber under various experimental conditions. Measurements were performed under calibration conditions and run conditions, which are distinguished by the flow rate of fresh air and trace gases entering the chamber at 20 and up to 210 L min−1, respectively. During steady-state calibration runs between −70 and +20 °C, the air temperature uniformity is better than ±0.06 °C in the radial direction and ±0.1 °C in the vertical direction. Larger non-uniformities are present during experimental runs, depending on the temperature control of the make-up air and trace gases (since some trace gases require elevated temperatures until injection into the chamber). The temperature stability is ±0.04 °C over periods of several hours during either calibration or steady-state run conditions. During rapid adiabatic expansions to activate cloud droplets and ice particles, the chamber walls are up to 10 °C warmer than the enclosed air. This results in temperature differences of ±1.5 °C in the vertical direction and ±1 °C in the horizontal direction, while the air returns to its equilibrium temperature with a time constant of about 200 s.

Single-particle mass spectrometry (SPMS) instruments characterize the composition of individual aerosol particles in real time. Their fundamental ability to differentiate the externally mixed particle types that constitute the atmospheric aerosol population enables a unique perspective into sources and transformation. However, quantitative measurements by SPMS systems are inherently problematic. We introduce a new technique that combines collocated measurements of aerosol composition by SPMS and size-resolved absolute particle concentrations on aircraft platforms. Quantitative number, surface area, volume, and mass concentrations are derived for climate-relevant particle types such as mineral dust, sea salt, and biomass burning smoke. Additionally, relative ion signals are calibrated to derive mass concentrations of internally mixed sulfate and organic material that are distributed across multiple particle types. The NOAA Particle Analysis by Laser Mass Spectrometry (PALMS) instrument measures size-resolved aerosol chemical composition from aircraft. We describe the identification and quantification of nine major atmospheric particle classes, including sulfate–organic–nitrate mixtures, biomass burning, elemental carbon, sea salt, mineral dust, meteoric material, alkali salts, heavy fuel oil combustion, and a remainder class. Classes can be sub-divided as necessary based on chemical heterogeneity, accumulated secondary material during aging, or other atmospheric processing. Concentrations are derived for sizes that encompass the accumulation and coarse size modes. A statistical error analysis indicates that particle class concentrations can be determined within a few minutes for abundances above ∼10 ng m−3. Rare particle types require longer sampling times. We explore the instrumentation requirements and the limitations of the method for airborne measurements. Reducing the size resolution of the particle data increases time resolution with only a modest increase in uncertainty. The principal limiting factor to fast time response concentration measurements is statistically relevant sampling across the size range of interest, in particular, sizes D µm for accumulation-mode studies and D > 2 µm for coarse-mode analysis. Performance is compared to other airborne and ground-based composition measurements, and examples of atmospheric mineral dust concentrations are given. The wealth of information afforded by composition-resolved size distributions for all major aerosol types represents a new and powerful tool to characterize atmospheric aerosol properties in a quantitative fashion.

Cloud condensation nuclei (CCN) can affect cloud properties and therefore Earth’s radiative balance1–3. New particle formation (NPF) from condensable vapours in the free troposphere has been suggested to contribute to CCN, especially in remote, pristine atmospheric regions4, but direct evidence is sparse, and the magnitude of this contribution is uncertain5–7. Here we use in situ aircraft measurements of vertical profiles of aerosol size distributions to present a global-scale survey of NPF occurrence. We observe intense NPF at high altitudes in tropical convective regions over both Pacific and Atlantic oceans. Together with the results of chemical-transport models, our findings indicate that NPF persists at all longitudes as a global-scale band in the tropical upper troposphere, covering about 40 per cent of Earth’s surface. Furthermore, we find that this NPF in the tropical upper troposphere is a globally important source of CCN in the lower troposphere, where CCN can affect cloud properties. Our findings suggest that the production of CCN as new particles descend towards the surface is not adequately captured in global models, which tend to underestimate both the magnitude of tropical upper tropospheric NPF and the subsequent growth of new particles to CCN sizes. Widespread formation of new particles from condensable vapours observed in the tropical upper troposphere is an important source of cloud condensation nuclei in the lower troposphere, affecting cloud properties.

We present the first data on the concentration of sea-salt aerosol throughout most of the depth of the troposphere and over a wide range of latitudes, which were obtained during the Atmospheric Tomography (ATom) mission. Sea-salt concentrations in the upper troposphere are very small, usually less than 10 ng per standard m3 (about 10 parts per trillion by mass) and often less than 1 ng m−3. This puts stringent limits on the contribution of sea-salt aerosol to halogen and nitric acid chemistry in the upper troposphere. Within broad regions the concentration of sea-salt aerosol is roughly proportional to water vapor, supporting a dominant role for wet scavenging in removing sea-salt aerosol from the atmosphere. Concentrations of sea-salt aerosol in the winter upper troposphere are not as low as in the summer and the tropics. This is mostly a consequence of less wet scavenging in the drier, colder winter atmosphere. There is also a source of sea-salt aerosol over pack ice that is distinct from that over open water. With a well-studied and widely distributed source, sea-salt aerosol provides an excellent test of wet scavenging and vertical transport of aerosols in chemical transport models.

Many of the particles in the troposphere are formed in situ but what fraction of all tropospheric particles do they constitute and how exactly are they made? Bianchi et al. report results from a high altitude research station. Roughly half of the particles were newly formed by the condensation of highly oxygenated multifunctional compounds. A combination of laboratory results field measurements and model calculations revealed that neutral nucleation is more than 10 times faster than ion induced nucleation that particle growth rates are size dependent and that new particle formation occurs during a limited time window.Science this issue p. 1109New particle formation (NPF) is the source of over half of the atmosphere’s cloud condensation nuclei thus influencing cloud properties and Earth’s energy balance. Unlike in the planetary boundary layer few observations of NPF in the free troposphere exist. We provide observational evidence that at high altitudes NPF occurs mainly through condensation of highly oxygenated molecules (HOMs) in addition to taking place through sulfuric acid–ammonia nucleation. Neutral nucleation is more than 10 times faster than ion induced nucleation and growth rates are size dependent. NPF is restricted to a time window of 1 to 2 days after contact of the air masses with the planetary boundary layer; this is related to the time needed for oxidation of organic compounds to form HOMs. These findings require improved NPF parameterization in atmospheric models.

Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia are thought to be the dominant processes responsible for new particle formation (NPF) in the cold temperatures of the middle and upper troposphere. Ions are also thought to be important for particle nucleation in these regions. However, global models presently lack experimentally measured NPF rates under controlled laboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here with data obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. The conditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrations between 5 × 105 and 1 × 109cm-3, and ammonia mixing ratios from zero added ammonia, i.e., nominally pure binary, to a maximumof ~1400 parts per trillion by volume (pptv).We performed nucleation studies under pure neutral conditions with zero ions being present in the chamber and at ionization rates of up to 75 ion pairs cm-3 s-1 to study neutral and ion-induced nucleation. We found that the contribution from ion-induced nucleation is small at temperatures between 208 and 248 K when ammonia is present at several pptv or higher. However, the presence of charges significantly enhances the nucleation rates, especially at 248 K with zero added ammonia, and for higher temperatures independent of NH3 levels.We compare these experimental data with calculated cluster formation rates from the Atmospheric Cluster Dynamics Code with cluster evaporation rates obtained from quantum chemistry.

International audience; The magnitude of aerosol radiative forcing caused by anthropogenic emissions depends on the baseline state of the atmosphere under Q:11 pristine preindustrial conditions. Measurements in the European Organisation for Nuclear Research (CERN) CLOUD chamber show that particle formation in atmospheric conditions can occur solely from Q:12 biogenic vapors. Here, we evaluate the potential effect of this source of particles on preindustrial cloud condensation nucleus (CCN) concentrations and aerosol cloud radiative forcing over the industrial period.Model simulations show that the pure biogenic particle formation mechanism has a much larger relative effect on CCN concentrations in the preindustrial atmosphere than in the present atmosphere because of the lower aerosol concentrations. Consequently, preindustrial cloud albedo is increased more than under present day conditions, and therefore, the cooling forcing of anthropogenic aerosols is reduced. Q:13 The mechanism increases CCN concentrations by 20–100% over a large fraction of the preindustrial lower atmosphere, and the magnitude of annual global mean radiative forcing caused by changes of cloud albedo since 1750 is reduced by 0.22 W m−² (27%) to −0.60 W m−².Model uncertainties, relatively slow formation rates, and limited available ambient measurements make it difficult to establish the significance of a mechanism that has its dominant effect under preindustrial conditions. Our simulations predict more particle formation in the Amazon than is observed. However, the first observation of pure organic nucleation has now been reported for the free troposphere. Given the potentially significant effect on anthropogenic forcing, effort should be made to better understand such naturally driven aerosol processes.

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere., The growth rates of freshly formed aerosol particles influence what fraction of these can reach sizes large enough to affect cloud formation and climate. Here, the authors show that the nano-particle growth in a sulphuric acid containing system can be enhanced by the presence of ions or small acid-base clusters.

New particle formation in the atmosphere produces around half of the cloud condensation nuclei that seed cloud droplets. Such particles have a pivotal role in determining the properties of clouds and the global radiation balance. Dunne et al. used the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN to construct a model of aerosol formation based on laboratory measured nucleation rates. They found that nearly all nucleation involves either ammonia or biogenic organic compounds. Furthermore in the present day atmosphere cosmic ray intensity cannot meaningfully affect climate via nucleation.Science this issue p. 1119Fundamental questions remain about the origin of newly formed atmospheric aerosol particles because data from laboratory measurements have been insufficient to build global models. In contrast gas phase chemistry models have been based on laboratory kinetics measurements for decades. We built a global model of aerosol formation by using extensive laboratory measurements of rates of nucleation involving sulfuric acid ammonia ions and organic compounds conducted in the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber. The simulations and a comparison with atmospheric observations show that nearly all nucleation throughout the present day atmosphere involves ammonia or biogenic organic compounds in addition to sulfuric acid. A considerable fraction of nucleation involves ions but the relatively weak dependence on ion concentrations indicates that for the processes studied variations in cosmic ray intensity do not appreciably affect climate through nucleation in the present day atmosphere.U http://science.sciencemag.org/content/sci/354/6316/1119.full.pdf

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., Nature, 533 (7604), ISSN:0028-0836, ISSN:1476-4687

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 classification 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.

We investigated the nucleation of sulfuric acid together with two bases (ammonia and dimethylamine), at the CLOUD chamber at CERN. The chemical composition of positive, negative, and neutral clusters was studied using three Atmospheric Pressure interface-Time Of Flight (APi-TOF) mass spectrometers: two were operated in positive and negative mode to detect the chamber ions, while the third was equipped with a nitrate ion chemical ionization source allowing detection of neutral clusters. Taking into account the possible fragmentation that can happen during the charging of the ions or within the first stage of the mass spectrometer, the cluster formation proceeded via essentially one-to-one acid-base addition for all of the clusters, independent of the type of the base. For the positive clusters, the charge is carried by one excess protonated base, while for the negative clusters it is carried by a deprotonated acid; the same is true for the neutral clusters after these have been ionized. During the experiments involving sulfuric acid and dimethylamine, it was possible to study the appearance time for all the clusters (positive, negative, and neutral). It appeared that, after the formation of the clusters containing three molecules of sulfuric acid, the clusters grow at a similar speed, independent of their charge. The growth rate is then probably limited by the arrival rate of sulfuric acid or cluster-cluster collision.

Amines at typical atmospheric concentrations of a only few molecules per trillion air molecules combine with sulphuric acid to form highly stable aerosol particles at rates similar to those observed in the lower atmosphere. Supplementary information The online version of this article (doi:10.1038/nature12663) contains supplementary material, which is available to authorized users., Atmospheric chemistry of anthropogenic amines Amines emitted into the atmosphere from anthropogenic sources are thought to enhance nucleation from trace atmospheric vapours, stimulate particle formation and influence the development and properties of clouds. Direct evidence for this under atmospheric conditions has been lacking; however, this study, using the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN, demonstrates that amines at atmospherically relevant concentrations can sufficiently increase nucleation rates to be able to account for the particle formation rates observed in the atmospheric environment. Supplementary information The online version of this article (doi:10.1038/nature12663) contains supplementary material, which is available to authorized users., Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei1. Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes2. Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases2. However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere3. It is thought that amines may enhance nucleation4,5,6,7,8,9,10,11,12,13,14,15,16, but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid–amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid–dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation. Supplementary information The online version of this article (doi:10.1038/nature12663) contains supplementary material, which is available to authorized users.

Understanding the vertical distribution of aerosol helps to reduce the uncertainty in the aerosol life cycle and therefore in the estimation of the direct and indirect aerosol forcing. To improve our understanding, we use measurements from four deployments of the Atmospheric Tomography (ATom) field campaign (ATom1–4) which systematically sampled aerosol and trace gases over the Pacific and Atlantic oceans with near pole-to-pole coverage. We evaluate the UK Earth System Model (UKESM1) against ATom observations in terms of joint biases in the vertical profile of three variables related to new particle formation: total particle number concentration (NTotal), sulfur dioxide (SO2) mixing ratio and the condensation sink. The NTotal, SO2 and condensation sink are interdependent quantities and have a controlling influence on the vertical profile of each other; therefore, analysing them simultaneously helps to avoid getting the right answer for the wrong reasons. The simulated condensation sink in the baseline model is within a factor of 2 of observations, but the NTotal and SO2 show much larger biases mainly in the tropics and high latitudes. We performed a series of model sensitivity tests to identify atmospheric processes that have the strongest influence on overall model performance. The perturbations take the form of global scaling factors or improvements to the representation of atmospheric processes in the model, for example by adding a new boundary layer nucleation scheme. In the boundary layer (below 1 km altitude) and lower troposphere (1–4 km), inclusion of a boundary layer nucleation scheme (Metzger et al., 2010) is critical to obtaining better agreement with observations. However, in the mid (4–8 km) and upper troposphere (> 8 km), sub-3 nm particle growth, pH of cloud droplets, dimethyl sulfide (DMS) emissions, upper-tropospheric nucleation rate, SO2 gas-scavenging rate and cloud erosion rate play a more dominant role. We find that perturbations to boundary layer nucleation, sub-3 nm growth, cloud droplet pH and DMS emissions reduce the boundary layer and upper tropospheric model bias simultaneously. In a combined simulation with all four perturbations, the SO2 and condensation sink profiles are in much better agreement with observations, but the NTotal profile still shows large deviations, which suggests a possible structural issue with how nucleation or gas/particle transport or aerosol scavenging is handled in the model. These perturbations are well-motivated in that they improve the physical basis of the model and are suitable for implementation in future versions of UKESM.