James N. Smith

Global atmospheric particle formation from CERN CLOUD measurements

Observations made in the CLOUD chamber at CERN illuminate atmospheric particle formation. How new particles form 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. 1119 Fundamental 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.

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron-sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid-catalyzed multiphase chemistry of isoprene epoxydiols, particle-phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process-related interactions, so that these processes can be accurately represented in atmospheric chemistry-climate models.

The Green Ocean Amazon Experiment (GoAmazon2014/5) Observes Pollution Affecting Gases, Aerosols, Clouds, and Rainfall over the Rain Forest

AbstractThe Observations and Modeling of the Green Ocean Amazon 2014–2015 (GoAmazon2014/5) experiment took place around the urban region of Manaus in central Amazonia across 2 years. The urban pollution plume was used to study the susceptibility of gases, aerosols, clouds, and rainfall to human activities in a tropical environment. Many aspects of air quality, weather, terrestrial ecosystems, and climate work differently in the tropics than in the more thoroughly studied temperate regions of Earth. GoAmazon2014/5, a cooperative project of Brazil, Germany, and the United States, employed an unparalleled suite of measurements at nine ground sites and on board two aircraft to investigate the flow of background air into Manaus, the emissions into the air over the city, and the advection of the pollution downwind of the city. Herein, to visualize this train of processes and its effects, observations aboard a low-flying aircraft are presented. Comparative measurements within and adjacent to the plume followed t...

On-Line Characterization of Morphology and Water Adsorption on Fumed Silica Nanoparticles

The first wetting layer on solid nanoparticles has direct implications on the roles these particles play in industrial processes and technological applications as well as in the atmosphere. We present a technique for online measurements of the adsorption of the first few water layers onto insoluble aerosol nanoparticles. Atomized fumed silica nanoparticles were dispersed from aqueous suspension and their hygroscopic growth factors (HGF) and number of the adsorbed water layers at subsaturated conditions were measured using a nanometer hygroscopic tandem differential mobility analyzer (HTDMA). Particle morphology was characterized by electron microscopy and particle density was determined by mobility analysis. The HGFs of the size-selected particles at mobility diameters from 10 to 50 nm at 90% relative humidity (RH) varied from 1.05 to 1.24, corresponding to 2–6 layers of adsorbed water. The morphology of the generated fumed silica nanoparticles varied from spheres at 8–10 nm to agglomerates at larger diameters with effective density from 1.7 to 0.8 g/cm3 and fractal dimension of 2.6. The smallest spheres and agglomerates had the highest HGFs. The smallest particles with diameters of 8 and 10 nm adsorbed two to three water layers in subsaturated conditions, which agreed well with the Frenkel, Halsey, and Hill (FHH) isotherm fitting. In comparison to the small spheres or large agglomerates, the compact agglomerate structure containing a few primary particles increased the number of adsorbed water layers by a factor of ∼1.5. This was probably caused by the capillary effect on the small cavities between the primary particles in the agglomerate.

Identification and quantification of particle growth channels during new particle formation

Atmospheric new particle formation (NPF) is a key source of ambient ultrafine particles that may contribute substantially to the global production of cloud condensation nuclei (CCN). While NPF is driven by atmospheric nucle- ation, its impact on CCN concentration depends strongly on atmospheric growth mechanisms since the growth rate must exceed the loss rate due to scavenging in order for the parti- cles to reach the CCN size range. In this work, chemical com- position measurements of 20 nm diameter particles during NPF in Hyytiala, Finland, in March-April 2011 permit iden- tification and quantitative assessment of important growth channels. In this work we show the following: (A) sulfuric acid, a key species associated with atmospheric nucleation, accounts for less than half of particle mass growth during this time period; (B) the sulfate content of a growing parti- cle during NPF is quantitatively explained by condensation of gas-phase sulfuric acid molecules (i.e., sulfuric acid up- take is collision-limited); (C) sulfuric acid condensation sub- stantially impacts the chemical composition of preexisting nanoparticles before new particles have grown to a size suffi- cient to be measured; (D) ammonium and sulfate concentra- tions are highly correlated, indicating that ammonia uptake is driven by sulfuric acid uptake; (E) sulfate neutralization by ammonium does not reach the predicted thermodynamic end point, suggesting that a barrier exists for ammonia up- take; (F) carbonaceous matter accounts for more than half of the particle mass growth, and its oxygen-to-carbon ratio ( 0.5) is characteristic of freshly formed secondary organic aerosol; and (G) differences in the overall growth rate from one formation event to another are caused by variations in the growth rates of all major chemical species, not just one individual species.

Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry.

Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

Modeling the thermodynamics and kinetics of sulfuric acid-dimethylamine-water nanoparticle growth in the CLOUD chamber

ABSTRACT Dimethylamine (DMA) has a stabilizing effect on sulfuric acid (SA) clusters, and the SA and DMA molecules and clusters likely play important roles in both aerosol particle formation and growth in the atmosphere. We use the monodisperse particle growth model for acid-base chemistry in nanoparticle growth (MABNAG) together with direct and indirect observations from the CLOUD4 and CLOUD7 experiments in the cosmics leaving outdoor droplets (CLOUD) chamber at CERN to investigate the size and composition evolution of freshly formed particles consisting of SA, DMA, and water as they grow to 20 nm in dry diameter. Hygroscopic growth factors are measured using a nano-hygroscopicity tandem differential mobility analyzer (nano-HTDMA), which combined with simulations of particle water uptake using the thermodynamic extended-aerosol inorganics model (E-AIM) constrain the chemical composition. MABNAG predicts a particle-phase ratio between DMA and SA molecules of 1.1–1.3 for a 2 nm particle and DMA gas-phase mixing ratios between 3.5 and 80 pptv. These ratios agree well with observations by an atmospheric-pressure interface time-of-flight (APi-TOF) mass spectrometer. Simulations with MABNAG, direct observations of the composition of clusters <2 nm, and indirect observations of the particle composition indicate that the acidity of the nucleated particles decreases as they grow from ∼1 to 20 nm. However, MABNAG predicts less acidic particles than suggested by the indirect estimates at 10 nm diameter using the nano-HTDMA measurements, and less acidic particles than observed by a thermal desorption chemical ionization mass spectrometer (TDCIMS) at 10–30 nm. Possible explanations for these discrepancies are discussed. Copyright

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range

Significance Aerosol particles can form and grow by gas-to-particle conversion and eventually act as seeds for cloud droplets, influencing global climate. Volatile organic compounds emitted from plants are oxidized in the atmosphere, and the resulting products drive particle growth. We measure particle growth by oxidized biogenic vapors with a well-controlled laboratory setup over a wide range of tropospheric temperatures. While higher temperatures lead to increased reaction rates and concentrations of highly oxidized molecules, lower temperatures allow additional, but less oxidized, species to condense. We measure rapid growth over the full temperature range of our study, indicating that organics play an important role in aerosol growth throughout the troposphere. Our finding will help to sharpen the predictions of global aerosol models. 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.

Evidence for Diverse Biogeochemical Drivers of Boreal Forest New Particle Formation

Author(s): Lawler, Michael J; Rissanen, Matti P; Ehn, Mikael; III, Mauldin R Lee; Sarnela, Nina; Sipila, Mikko; Smith, James N

Size resolved chemical composition of nanoparticles from reactions of sulfuric acid with ammonia and dimethylamine

Abstract Nanoparticle formation and growth driven by acid-base chemistry was investigated by introducing gas-phase sulfuric acid (H2SO4) with ammonia (NH3) or dimethylamine (DMA) into a flow tube reactor. A thermal desorption chemical Ionization mass spectrometer was used to measure the size-resolved chemical composition of H2SO4-DMA and H2SO4- NH3 nanoparticles formed under dry conditions and at 60% relative humidity. In contrast with predictions for bulk aqueous systems, nanoparticles showed a strong size-dependent composition gradient and did not always reach a fully neutralized state in excess of gas-phase base. Smaller particles were more acidic, with an acid:base ratio of 0.7 ± 0.1 and 1.3 ± 0.3 for 8.6 and 9.5 nm H2SO4-DMA particles formed under dry and humid conditions, respectively, and 3.1 ± 0.6 and 3.4 ± 0.3 for 7.5 nm H2SO4-NH3 particles formed under dry and humid conditions, respectively. The acidity of particles generally decreased as particles grew. H2SO4-DMA particles became fully neutralized as they grew to 14 nm, but H2SO4-NH3 particles at 12 nm were still acidic and were never observed to reach bulk sample thermodynamic equilibrium for the experimental conditions in this study. Thermodynamic modeling demonstrated that the observed trends can be reproduced by modifying acid dissociation constants to minimize acid-base chemistry, which may be caused by steric or mixing effects, and by considering volatilization of the neutral base. Copyright