The SAWNUC (Sulphuric Acid Water NUCleation) microphysical aerosol nucleation model is used to study the effect of reactor walls on the interpretation of nucleation experiments with respect to ...nucleation theory. This work shows that loss processes, such as wall losses, influence the interpretation of nucleation experiments, especially at low growth rates and short lifetimes of freshly nucleated particles. In these cases the power dependency of the formation rates, determined at a certain particle size, with respect to H2SO4 does not correspond to the approximate number of H2SO4 molecules in the critical cluster as expected by the first nucleation theorem. Observed ∂log(J)/∂log(H2SO4) therefore can vary widely for identical nucleation conditions but different sink terms.
Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of ...atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene) showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene. New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ), defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.
The performance of an ion source based on corona discharge has been studied. This source is used for the detection of gaseous sulfuric acid by chemical ionization mass spectrometry (CIMS) through the ...reaction of NO3– ions with H2SO4. The ion source is operated under atmospheric pressure and its design is similar to the one of a radioactive (americium-241) ion source which has been used previously. The results show that the detection limit for the corona ion source is sufficiently good for most applications. For an integration time of 1 min it is ~6 × 104 molecule cm−3 of H2SO4. In addition, only a small cross-sensitivity to SO2 has been observed for concentrations as high as 1 ppmv in the sample gas. This low sensitivity to SO2 is achieved even without the addition of an OH scavenger. When comparing the new corona ion source with the americium ion source for the same provided H2SO4 concentration, both ion sources yield almost identical values. These features make the corona ion source investigated here favorable over the more commonly used radioactive ion sources for most applications where H2SO4 is measured by CIMS.
Over the last few years, several condensation particle counters (CPCs) capable of measuring in the sub-3 nm size range have been developed. Here we study the performance of CPCs based on diethylene ...glycol (DEG) at different temperatures during Cosmics Leaving OUtdoor Droplets (CLOUD) measurements at CERN. The data shown here are the first set of verification measurements for sub-3 nm CPCs under upper tropospheric temperatures using atmospherically relevant aerosol particles. To put the results in perspective we calibrated the DEG-CPC at room temperature, resulting in a cut-off diameter of 1.4 nm. All diameters refer to mobility equivalent diameters in this paper. At upper tropospheric temperatures ranging from 246.15 K to 207.15 K, we found cut-off sizes relative to a particle size magnifier in the range of 2.5 to 2.8 nm. Due to low number concentration after size classification, the cut-off diameters have a high uncertainty (±0.3 nm) associated with them. Operating two laminar flow DEG-CPCs with different cut-off sizes together with other aerosol instruments, we looked at the growth rates of aerosol population in the CLOUD chamber for particles smaller than 10 nm at different temperatures. A more consistent picture emerged when we normalized the growth rates to a fixed gas-phase sulfuric acid concentration. All of the instruments detected larger growth rates at lower temperatures, and the observed growth rates decreased as a function of temperature, showing a similar trend for all instruments. The theoretical calculations had a similar but much smaller temperature dependency.
We present the results of laboratory measurements of the ion-ion recombination coefficient at different temperatures, relative humidities and concentrations of ozone and sulfur dioxide. The ...experiments were carried out using the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at CERN, the walls of which are made of conductive material, making it possible to measure small ions. We produced ions in the chamber using a 3.5 GeV c-1 beam of positively charged pions ( pi +) generated by the CERN Proton Synchrotron (PS). When the PS was switched off, galactic cosmic rays were the only ionization source in the chamber. The range of the ion production rate varied from 2 to 100 cm-3 s-1, covering the typical range of ionization throughout the troposphere. The temperature ranged from -55 to 20 degree C, the relative humidity (RH) from 0 to 70 %, the SO2 concentration from 0 to 40 ppb, and the ozone concentration from 200 to 700 ppb. The best agreement of the retrieved ion-ion recombination coefficient with the commonly used literature value of 1.6 10-6 cm3 s-1 was found at a temperature of 5 degree C and a RH of 40 % (1.5 plus or minus 0.6) 10-6 cm3 s-1. At 20 degree C and 40 % RH, the retrieved ion-ion recombination coefficient was instead (2.3 plus or minus 0.7) 10-6 cm3 s-1. We observed no dependency of the ion-ion recombination coefficient on ozone concentration and a weak variation with sulfur dioxide concentration. However, we observed a more than fourfold increase in the ion-ion recombination coefficient with decreasing temperature. We compared our results with three different models and found an overall agreement for temperatures above 0 degree C, but a disagreement at lower temperatures. We observed a strong increase in the recombination coefficient for decreasing relative humidities, which has not been reported previously.
Sulfuric acid, amines and oxidized organics have been found to be important compounds in the nucleation and initial growth of atmospheric particles. Because of the challenges involved in determining ...the chemical composition of objects with very small mass, however, the properties of the freshly nucleated particles and the detailed pathways of their formation processes are still not clear. In this study, we focus on a challenging size range, i.e., particles that have grown to diameters of 10 and 15 nm following nucleation, and measure their water uptake. Water uptake is useful information for indirectly obtaining chemical composition of aerosol particles. We use a nanometer-hygroscopicity tandem differential mobility analyzer (nano-HTDMA) at subsaturated conditions (ca. 90 % relative humidity at 293 K) to measure the hygroscopicity of particles during the seventh Cosmics Leaving OUtdoor Droplets (CLOUD7) campaign performed at CERN in 2012. In CLOUD7, the hygroscopicity of nucleated nanoparticles was measured in the presence of sulfuric acid, sulfuric acid–dimethylamine, and sulfuric acid–organics derived from α-pinene oxidation. The hygroscopicity parameter κ decreased with increasing particle size, indicating decreasing acidity of particles. No clear effect of the sulfuric acid concentration on the hygroscopicity of 10 nm particles produced from sulfuric acid and dimethylamine was observed, whereas the hygroscopicity of 15 nm particles sharply decreased with decreasing sulfuric acid concentrations. In particular, when the concentration of sulfuric acid was 5.1 × 106 molecules cm−3 in the gas phase, and the dimethylamine mixing ratio was 11.8 ppt, the measured κ of 15 nm particles was 0.31 ± 0.01: close to the value reported for dimethylaminium sulfate (DMAS) (κDMAS ∼ 0.28). Furthermore, the difference in κ between sulfuric acid and sulfuric acid–imethylamine experiments increased with increasing particle size. The κ values of particles in the presence of sulfuric acid and organics were much smaller than those of particles in the presence of sulfuric acid and dimethylamine. This suggests that the organics produced from α-pinene ozonolysis play a significant role in particle growth even at 10 nm sizes.
Ternary aerosol nucleation experiments were conducted in the CLOUD chamber at CERN in order to investigate the influence of ions on new particle formation. Neutral and ion-induced nucleation ...experiments, i.e. without and with the presence of ions, respectively, were carried out under precisely controlled conditions. The sulfuric acid concentration was measured with a chemical ionisation mass spectrometer (CIMS) during the new particle formation experiments. The added ternary trace gases were ammonia (NH3), dimethylamine (DMA, C2H7N) or oxidised products of pinanediol (PD, C10H18O2). When pinanediol was introduced into the chamber, an increase in the mass spectrometric signal used to determine the sulfuric acid concentration (m/z 97, i.e. HSO4−) was observed due to ions from the CLOUD chamber. The enhancement was only observed during ion-induced nucleation measurements by using either galactic cosmic rays (GCRs) or the proton synchrotron (PS) pion beam for the ion generation, respectively. The ion effect typically involved an increase in the apparent sulfuric acid concentration by a factor of ~ 2 to 3 and was qualitatively verified by the ion measurements with an atmospheric-pressure interface-time of flight (APi-TOF) mass spectrometer. By applying a high-voltage (HV) clearing field inside the CLOUD chamber, the ion effect on the CIMS measurement was completely eliminated since, under these conditions, small ions are swept from the chamber in about 1 s. In order to exclude the ion effect and to provide corrected sulfuric acid concentrations during the GCR and PS beam nucleation experiments, a parameterisation was derived that utilises the trace gas concentrations and the UV light intensity as input parameters. Atmospheric sulfuric acid measurements with a CIMS showed an insignificant ion effect.
A new global dataset of annually averaged ultrafine particle (UFP) concentrations at the Earth's surface for the years 2015–2017 has been developed through numerical simulations using the ECHAM/MESSy ...Atmospheric Chemistry model (EMAC). We present total and size-resolved concentrations along with their interannual variability. Size distributions of emitted particles from the contributing source sectors have been derived based on literature reports. The model results of UFP concentrations are evaluated using particle size distribution and particle number concentration measurements from available datasets and the literature. While we obtain reasonable agreement between the model results and observations (logarithmic-scale correlation of r=0.76 for non-remote, polluted regions), the highest values of observed, street-level UFP concentrations are systematically underestimated, whereas in rural environments close to urban areas the model generally overestimates observed UFP concentrations. As the relatively coarse global model does not resolve concentration gradients in urban centres and industrial UFP hotspots, high-resolution data of anthropogenic emissions are used to account for such differences in each model grid box, obtaining UFP concentrations with unprecedented 0.1∘×0.1∘ horizontal resolution at the Earth's surface. This observation-guided downscaling further improves the agreement with observations, leading to an increase in the logarithmic-scale correlation between observed and simulated UFP concentrations to r=0.84 in polluted environments (and 0.95 in all regions), a decrease in the root mean squared logarithmic error (from 0.57 to 0.43), and removal of discrepancies associated with air quality and population density gradients within the model grid boxes. The model results are made publicly available for studies on public health and other impacts of atmospheric UFPs, as well as for intercomparison with other regional and global models and datasets.
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