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Ambient aerosol size distributions obtained with a compact scanning mobility analyzer, the “Spider” differential mobility analyzer (DMA), are compared to those obtained with a conventional mobility analyzer, with specific attention to the effect of mobility resolution on the measured size distribution parameters. The Spider is a 12 cm diameter radial differential mobility analyzer that spans the 10–500 nm size range with 30 s mobility scans. It achieves its compact size by operating at a nominal mobility resolution R=3 (sheath flow = 0.9 L min−1; aerosol flow = 0.3 L min−1) in place of the higher ratio of sheath flow to aerosol flow commonly used. The question addressed here is whether the lower resolution is sufficient to capture key characteristics of ambient aerosol size distributions. The Spider, operated at R=3 with 30 s up- and downscans, was co-located with a TSI 3081 long-column mobility analyzer, operated at R=10 with a 360 s sampling duty cycle. Ambient aerosol data were collected over 26 consecutive days of continuous operation, in Pasadena, CA. Over the 17–500 nm size range, the two instruments exhibit excellent correlation in the total particle number concentrations and geometric mean diameters, with regression slopes of 1.13 and 1.00, respectively. Our results suggest that particle sizing at a lower resolution than typically employed may be sufficient to obtain key properties of ambient size distributions, at least for these two moments of the size distribution. Moreover, it enables better counting statistics, as the wider transfer function for a given aerosol flow rate results in a higher counting rate.

Publisher Copyright: © 2021 Mao Xiao et al. New particle formation (NPF) is a significant source of atmospheric particles, affecting climate and air quality. Understanding the mechanisms involved in urban aerosols is important to develop effective mitigation strategies. However, NPF rates reported in the polluted boundary layer span more than 4 orders of magnitude, and the reasons behind this variability are the subject of intense scientific debate. Multiple atmospheric vapours have been postulated to participate in NPF, including sulfuric acid, ammonia, amines and organics, but their relative roles remain unclear. We investigated NPF in the CLOUD chamber using mixtures of anthropogenic vapours that simulate polluted boundary layer conditions. We demonstrate that NPF in polluted environments is largely driven by the formation of sulfuric acid-base clusters, stabilized by the presence of amines, high ammonia concentrations and lower temperatures. Aromatic oxidation products, despite their extremely low volatility, play a minor role in NPF in the chosen urban environment but can be important for particle growth and hence for the survival of newly formed particles. Our measurements quantitatively account for NPF in highly diverse urban environments and explain its large observed variability. Such quantitative information obtained under controlled laboratory conditions will help the interpretation of future ambient observations of NPF rates in polluted atmospheres.

Particle size measurement in the low nanometer regime is of great importance to the study of cloud condensation nuclei formation and to better understand aerosol–cloud interactions. Here we present the design, modeling, and experimental characterization of the nano-scanning electrical mobility spectrometer (nSEMS), a recently developed instrument that probes particle physical properties in the 1.5–25 nm range. The nSEMS consists of a novel differential mobility analyzer and a two-stage condensation particle counter (CPC). The mobility analyzer, a radial opposed-migration ion and aerosol classifier (ROMIAC), can classify nanometer-sized particles with minimal degradation of its resolution and diffusional losses. The ROMIAC operates on a dual high-voltage supply with fast polarity-switching capability to minimize sensitivity to variations in the chemical nature of the ions used to charge the aerosol. Particles transmitted through the mobility analyzer are measured using a two-stage CPC. They are first activated in a fast-mixing diethylene glycol (DEG) stage before being counted by a second detection stage, an ADI MAGIC™ water-based CPC. The transfer function of the integrated instrument is derived from both finite-element modeling and experimental characterization. The nSEMS performance has been evaluated during measurement of transient nucleation and growth events in the CLOUD atmospheric chamber at CERN. We show that the nSEMS can provide high-time- and size-resolution measurement of nanoparticles and can capture the critical aerosol dynamics of newly formed atmospheric particles. Using a soft x-ray bipolar ion source in a compact housing designed to optimize both nanoparticle charging and transmission efficiency as a charge conditioner, the nSEMS has enabled measurement of the contributions of both neutral and ion-mediated nucleation to new particle formation.

Aerosol–cloud interactions are the largest source of uncertainty in quantifying anthropogenic radiative forcing. The large uncertainty is, in part, due to the difficulty of predicting cloud microphysical parameters, such as the cloud droplet number concentration (Nd). Even though rigorous first-principle approaches exist to calculate Nd, the cloud and aerosol research community also relies on empirical approaches such as relating Nd to aerosol mass concentration. Here we analyze relationships between Nd and cloud water chemical composition, in addition to the effect of environmental factors on the degree of the relationships. Warm, marine, stratocumulus clouds off the California coast were sampled throughout four summer campaigns between 2011 and 2016. A total of 385 cloud water samples were collected and analyzed for 80 chemical species. Single- and multispecies log–log linear regressions were performed to predict Nd using chemical composition. Single-species regressions reveal that the species that best predicts Nd is total sulfate (Radj2=0.40). Multispecies regressions reveal that adding more species does not necessarily produce a better model, as six or more species yield regressions that are statistically insignificant. A commonality among the multispecies regressions that produce the highest correlation with Nd was that most included sulfate (either total or non-sea-salt), an ocean emissions tracer (such as sodium), and an organic tracer (such as oxalate). Binning the data according to turbulence, smoke influence, and in-cloud height allowed for examination of the effect of these environmental factors on the composition–Nd correlation. Accounting for turbulence, quantified as the standard deviation of vertical wind speed, showed that the correlation between Nd with both total sulfate and sodium increased at higher turbulence conditions, consistent with turbulence promoting the mixing between ocean surface and cloud base. Considering the influence of smoke significantly improved the correlation with Nd for two biomass burning tracer species in the study region, specifically oxalate and iron. When binning by in-cloud height, non-sea-salt sulfate and sodium correlated best with Nd at cloud top, whereas iron and oxalate correlated best with Nd at cloud base.

Discontinuities in apparent hygroscopicity below and above water saturation have been observed for organic and mixed organic–inorganic aerosol particles in both laboratory studies and in the ambient atmosphere. However, uncertainty remains regarding the factors that contribute to observations of low hygroscopic growth below water saturation but enhanced cloud condensation nuclei (CCN) activity for a given aerosol population. Utilizing laboratory surrogates for oligomers in atmospheric aerosols, we explore the extent to which such discontinuities are influenced by organic component molecular mass and viscosity, non-ideal thermodynamic interactions between aerosol components, and the combination of these factors. Measurements of hygroscopic growth under subsaturated conditions and the CCN activity of aerosols comprised of polyethylene glycol (PEG) with average molecular masses ranging from 200 to 10 000 g mol−1 and mixtures of PEG with ammonium sulfate (AS) were conducted. Experimental results are compared to calculations of hygroscopic growth at thermodynamic equilibrium conducted with the Aerosol Inorganic Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model, and the potential influence of kinetic limitations on observed water uptake was further explored through estimations of water diffusivity in the PEG oligomers. Particle-phase behavior, including the prevalence of liquid–liquid phase separation (LLPS), was also modeled with AIOMFAC. Under subsaturated relative humidity (RH) conditions, we observed little variability in hygroscopic growth across PEG systems with different molecular masses; however, an increase in CCN activity with increasing PEG molecular mass was observed. This effect is most pronounced for PEG–AS mixtures, and, in fact, an enhancement in CCN activity was observed for the PEG10000–AS mixture as compared to pure AS, as evidenced by a 15 % reduction in critical activation diameter at a supersaturation of 0.8 %. We also observed a marked increase in apparent hygroscopicity for mixtures of higher molecular mass PEG and AS under supersaturated conditions as compared to subsaturated hygroscopic growth. AIOMFAC-based predictions and estimations of water diffusivity in PEG suggest that such discontinuities in apparent hygroscopicity above and below water saturation can be attributed, at least in part, to differences in the sensitivity of water uptake behavior to surface tension effects. There is no evidence that kinetic limitations to water uptake due to the presence of viscous aerosol components influenced hygroscopic growth. For the systems that display an enhancement in apparent hygroscopicity above water saturation, LLPS is predicted to persist to high RH. This indicates a miscibility gap and is likely to influence bulk-to-surface partitioning of PEG at high RH, impacting droplet surface tension and CCN activity. This work provides insight into the factors likely to be contributing to discontinuities in aerosol water-uptake behavior below and above water saturation that have been observed previously in the ambient atmosphere.

It was recently shown by the CERN CLOUD experiment that biogenic highly oxygenated molecules (HOMs) form particles under atmospheric conditions in the absence of sulfuric acid, where ions enhance the nucleation rate by 1–2 orders of magnitude. The biogenic HOMs were produced from ozonolysis of α-pinene at 5 °C. Here we extend this study to compare the molecular composition of positive and negative HOM clusters measured with atmospheric pressure interface time-of-flight mass spectrometers (APi-TOFs), at three different temperatures (25, 5 and −25 °C). Most negative HOM clusters include a nitrate (NO3−) ion, and the spectra are similar to those seen in the nighttime boreal forest. On the other hand, most positive HOM clusters include an ammonium (NH4+) ion, and the spectra are characterized by mass bands that differ in their molecular weight by ∼ 20 C atoms, corresponding to HOM dimers. At lower temperatures the average oxygen to carbon (O : C) ratio of the HOM clusters decreases for both polarities, reflecting an overall reduction of HOM formation with decreasing temperature. This indicates a decrease in the rate of autoxidation with temperature due to a rather high activation energy as has previously been determined by quantum chemical calculations. Furthermore, at the lowest temperature (−25 °C), the presence of C30 clusters shows that HOM monomers start to contribute to the nucleation of positive clusters. These experimental findings are supported by quantum chemical calculations of the binding energies of representative neutral and charged clusters.

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 constrains their chemical composition. 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) experiments 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 monomer concentrations on the hygroscopicities 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 monomer concentrations. In particular, when the concentrations 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 dimethylamine sulfate (DMAS) (κDMAS ~ 0.28). Furthermore, the difference in κ between sulfuric acid and sulfuric acid-dimethylamine 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 already at 10 nm sizes.

The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.

Article, 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., published version, peerReviewed

Reliable and reproducible measurements of atmospheric aerosol particle number size distributions below 10 nm require optimized classification instruments with high particle transmission efficiency. Almost all DMAs have an unfavorable potential gradient at the outlet (e.g. long column, Vienna type) or at the inlet (nano-radial DMA). This feature prevents them from achieving a good transmission efficiency for the smallest nanoparticles. We developed a new high transmission inlet for the Caltech nano-radial DMA (nRDMA) that increases the transmission efficiency to 12 % for ions as small as 1.3 nm in mobility equivalent diameter (corresponding to 1.2 × 10−4 m2 V−1 s−1 in electrical mobility). We successfully deployed the nRDMA, equipped with the new inlet, in chamber measurements, using a Particle Size Magnifier (PSM) and a booster Condensation Particle Counter (CPC) as a counter. With this setup, we were able to measure size distributions of ions between 1.3 and 6 nm, corresponding to a mobility range from 1.2 × 10−4 to 5.8 × 10−6 m2 V−1 s−1. The system was modeled, tested in the laboratory and used to measure negative ions at ambient concentrations in the CLOUD 7 measurement campaign at CERN. We achieved a higher size resolution than techniques currently used in field measurements, and maintained a good transmission efficiency at moderate inlet and sheath air flows (2.5 and 30 LPM, respectively). In this paper, by measuring size distribution at high size resolution down to 1.3 nm, we extend the limit of the current technology. The current setup is limited to ion measurements. However, we envision that future research focused on the charging mechanisms could extend the technique to measure neutral aerosol particles as well, so that it will be possible to measure size distributions of ambient aerosols from 1 nm to 1 μm.

Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H2SO4-H2O) system, and the ternary system involving ammonia (H2SO4-H2O-NH3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a Chemical Ionization Mass Spectrometer (CIMS). From these measurements dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H2SO4 • NH3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H2SO4 • NH3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using Chemical Ionization-Atmospheric Pressure interface-Time Of Flight (CI-APi-TOF) mass spectrometry.

Recent work has demonstrated that organic and mixed organic–inorganic particles can exhibit multiple phase states depending on their chemical composition and on ambient conditions such as relative humidity (RH). To explore the extent to which water uptake varies with particle phase behavior, hygroscopic growth factors (HGFs) of nine laboratory-generated, organic and organic–inorganic aerosol systems with physical states ranging from well-mixed liquids, to phase-separated particles, to viscous liquids or semi-solids were measured with the Differential Aerosol Sizing and Hygroscopicity Spectrometer Probe at RH values ranging from 40–90%. Water-uptake measurements were accompanied by HGF and RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model. In addition, AIOMFAC-predicted growth curves are compared to several simplified HGF modeling approaches: (1) representing particles as ideal, well-mixed liquids, (2) forcing a single phase, but accounting for non-ideal interactions through activity coefficient calculations, and (3) a Zdanovskii–Stokes–Robinson-like calculation in which complete separation between the inorganic and organic components is assumed at all RH values, with water-uptake treated separately in each of the individual phases. We observed variability in the characteristics of measured hygroscopic growth curves across aerosol systems with differing phase behaviors, with growth curves approaching smoother, more continuous water uptake with decreasing prevalence of liquid–liquid phase separation and increasing oxygen : carbon ratios of the organic aerosol components. We also observed indirect evidence for the dehydration-induced formation of highly viscous semi-solid phases and for kinetic limitations to the crystallization of ammonium sulfate at low RH for sucrose-containing particles. AIOMFAC-predicted growth curves are generally in good agreement with the HGF measurements. The performances of the simplified modeling approaches, however, differ for particles with differing phase states. This suggests that a single simplified modeling approach cannot be used to capture the water-uptake behavior for the diversity of particle phase behavior expected in the atmosphere. Errors in HGFs calculated with the simplified models are of sufficient magnitude to contribute substantially to error in estimates of particle optical and radiative properties, particularly for the assumption that water uptake is driven by absorptive equilibrium partitioning with ideal particle-phase mixing.

In the present-day atmosphere, sulfuric acid is the most important vapour for aerosol particle formation and initial growth. However, the growth rates of nanoparticles ( nm) from sulfuric acid remain poorly measured. Therefore, the effect of stabilizing bases, the contribution of ions and the impact of attractive forces on molecular collisions are under debate. Here, we present precise growth rate measurements of uncharged sulfuric acid particles from 1.8 to 10 nm, performed under atmospheric conditions in the CERN (European Organization for Nuclear Research) CLOUD chamber. Our results show that the evaporation of sulfuric acid particles above 2 nm is negligible, and growth proceeds kinetically even at low ammonia concentrations. The experimental growth rates exceed the hard-sphere kinetic limit for the condensation of sulfuric acid. We demonstrate that this results from van der Waals forces between the vapour molecules and particles and disentangle it from charge–dipole interactions. The magnitude of the enhancement depends on the assumed particle hydration and collision kinetics but is increasingly important at smaller sizes, resulting in a steep rise in the observed growth rates with decreasing size. Including the experimental results in a global model, we find that the enhanced growth rate of sulfuric acid particles increases the predicted particle number concentrations in the upper free troposphere by more than 50 %.