Amplification of Arctic warming by past air pollution reductions in Europe
The role of low-volatility organic compounds in initial particle growth in the atmosphere
About half of present-day cloud condensation nuclei originate from atmospheric nucleation, frequently appearing as a burst of new particles near midday(1). Atmospheric observations show that the growth rate of new particles often accelerates when the diameter of the particles is between one and ten nanometres(2,3). In this critical size range, new particles are most likely to be lost by coagulation with pre-existing particles(4), 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 growth(5,6), leaving organic vapours as the most plausible alternative, at least in the planetary boundary layer(7-10). Although recent studies(11-13) 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 afternoon(2), and the presence of a possible Kelvin (curvature) effect, which inhibits organic vapour condensation on the smallest particles (the nano-Kohler 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 shown(15) 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.
Modeling the thermodynamics and kinetics of sulfuric acid-dimethylamine-water nanoparticle growth in the CLOUD chamber
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 20nm 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 2nm 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 <2nm, and indirect observations of the particle composition indicate that the acidity of the nucleated particles decreases as they grow from approximate to 1 to 20nm. However, MABNAG predicts less acidic particles than suggested by the indirect estimates at 10nm diameter using the nano-HTDMA measurements, and less acidic particles than observed by a thermal desorption chemical ionization mass spectrometer (TDCIMS) at 10-30nm. Possible explanations for these discrepancies are discussed.Copyright (c) 2016 American Association for Aerosol Research
Amplification of Arctic warming by past air pollution reductions in Europe (vol 9, pg 277, 2016)
Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD
New particle formation driven by acid-base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10-30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10 nm.
Wall effects in smog chamber experiments: A model study
Wall losses of condensable organic vapors are a significant complication for smog-chamber experiments designed to constrain production of Secondary Organic Aerosols (SOA). Here we develop a dynamical mass-balance model based on the Volatility Basis Set (VBS) to explore various pathways for mass transfer between the bulk of a smog-chamber volume (the vapors and suspended particles) and reservoirs near the chamber walls (deposited and/or nucleated particles on the walls, adsorption to the walls, and sorption into Teflon walls). We consider various limiting cases and explore the sensitivity of inferred SOA yields to assumptions about the actual parameters in a given SOA experiment. We also present data suggesting that adsorptive uptake to Teflon for typical SOA is modest. Broadly, we find that walls become a sink for condensable vapors when those vapors interact with either deposited particles of the Teflon walls, with qualitatively similar effects on the suspended particles. Finally, we show that having a relatively high seed condensation sink is vital to reliable chamber mass balances.
Implementation of state-of-the-art ternary new-particle formation scheme to the regional chemical transport model PMCAMx-UF in Europe
The particle formation scheme within PMCAMx-UF, a three-dimensional chemical transport model, was updated with particle formation rates for the ternary H2SO4-NH3-H2O pathway simulated by the Atmospheric Cluster Dynamics Code (ACDC) using quantum chemical input data. The model was applied over Europe for May 2008, during which the EUCAARI-LONGREX (European Aerosol Cloud Climate and Air Quality Interactions-Long-Range Experiment) campaign was carried out, providing aircraft vertical profiles of aerosol number concentrations. The updated model reproduces the observed number concentrations of particles larger than 4 nm within 1 order of magnitude throughout the atmospheric column. This agreement is encouraging considering the fact that no semi-empirical fitting was needed to obtain realistic particle formation rates. The cloud adjustment scheme for modifying the photolysis rate profiles within PMCAMx-UF was also updated with the TUV (Tropospheric Ultraviolet and Visible) radiative-transfer model. Results show that, although the effect of the new cloud adjustment scheme on total number concentrations is small, enhanced new-particle formation is predicted near cloudy regions. This is due to the enhanced radiation above and in the vicinity of the clouds, which in turn leads to higher production of sulfuric acid. The sensitivity of the results to including emissions from natural sources is also discussed.
Surface Partitioning in Organic-Inorganic Mixtures Contributes to the Size-Dependence of the Phase-State of Atmospheric Nanoparticles
Atmospheric particulate matter is one of the main factors governing the Earth's radiative budget, but its exact effects on the global climate are still uncertain. Knowledge on the molecular-scale surface phenomena as well as interactions between atmospheric organic and inorganic compounds is necessary for understanding the role of airborne nanoparticles in the Earth system. In this work, surface composition of aqueous model systems containing succinic acid and sodium chloride or ammonium sulfate is determined using a novel approach combining X-ray photoelectron spectroscopy, surface tension measurements and thermodynamic modeling. It is shown that succinic acid molecules are accumulated in the surface, yielding a 10-fold surface concentration as compared with the bulk for saturated succinic acid solutions. Inorganic salts further enhance this enrichment due to competition for hydration in the bulk. The surface compositions for various mixtures are parametrized to yield generalizable results and used to explain changes in surface tension. The enhanced surface partitioning implies an increased maximum solubility of organic compounds in atmospheric nanoparticles. The results can explain observations of size-dependent phase-state of atmospheric nanoparticles, suggesting that these particles can display drastically different behavior than predicted by bulk properties only.
An empirically derived inorganic sea spray source function incorporating sea surface temperature
We have developed an inorganic sea spray source function that is based upon state-of-the-art measurements of sea spray aerosol production using a temperature-controlled plunging jet sea spray aerosol chamber. The size-resolved particle production was measured between 0.01 and 10 μm dry diameter. Particle production decreased non-linearly with increasing seawater temperature (between −1 and 30 °C) similar to previous findings. In addition, we observed that the particle effective radius, as well as the particle surface, particle volume and particle mass, increased with increasing seawater temperature due to increased production of particles with dry diameters greater than 1 μm. By combining these measurements with the volume of air entrained by the plunging jet we have determined the size-resolved particle flux as a function of air entrainment. Through the use of existing parameterisations of air entrainment as a function of wind speed, we were subsequently able to scale our laboratory measurements of particle production to wind speed. By scaling in this way we avoid some of the difficulties associated with defining the "white area" of the laboratory whitecap – a contentious issue when relating laboratory measurements of particle production to oceanic whitecaps using the more frequently applied whitecap method.
The here-derived inorganic sea spray source function was implemented in a Lagrangian particle dispersion model (FLEXPART – FLEXible PARTicle dispersion model). An estimated annual global flux of inorganic sea spray aerosol of 5.9 ± 0.2 Pg yr−1 was derived that is close to the median of estimates from the same model using a wide range of existing sea spray source functions. When using the source function derived here, the model also showed good skill in predicting measurements of Na+ concentration at a number of field sites further underlining the validity of our source function.
In a final step, the sensitivity of a large-scale model (NorESM – the Norwegian Earth System Model) to our new source function was tested. Compared to the previously implemented parameterisation, a clear decrease of sea spray aerosol number flux and increase in aerosol residence time was observed, especially over the Southern Ocean. At the same time an increase in aerosol optical depth due to an increase in the number of particles with optically relevant sizes was found. That there were noticeable regional differences may have important implications for aerosol optical properties and number concentrations, subsequently also affecting the indirect radiative forcing by non-sea spray anthropogenic aerosols.