New 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.
The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which ...vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH sub(3)) and sulfuric acid (H sub(2)SO sub(4)). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH sub(3)-H sub(2)SO sub(4) clusters over a wide range of atmospherically relevant environmental conditions. We covered NH sub(3) in the range from < 2 to 1400 pptv, H sub(2)SO sub(4) from 3.3 x 10 super(6) to 1.4 x 10 super(9) cm super(-3) (0.1 to 56 pptv), and a temperature range from -25 to +20 degree C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH sub(3) and H sub(2)SO sub(4), and then grew to larger clusters containing more than 50 molecules of NH sub(3) and H sub(2)SO sub(4), corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH sub(3)-H sub(2)SO sub(4) clusters is primarily determined by the ratio of gas-phase concentrations NH sub(3) / H sub(2)SO sub(4), as well as by temperature. Pure binary H sub(2)O-H sub(2)SO sub(4) clusters (observed as clusters of only H sub(2)SO sub(4)) only form at NH sub(3) / H sub(2)SO sub(4) < 0.1 to 1. For larger values of NH sub(3) / H sub(2)SO sub(4), the composition of NH sub(3)-H sub(2)SO sub(4) clusters was characterized by the number of NH sub(3) molecules m added for each added H sub(2)SO sub(4) molecule n ( Delta m/ Delta n), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Delta m/ Delta n saturated between 1 and 1.4 for NH sub(3) / H sub(2)SO sub(4) > 10. Positively charged clusters grew on average by Delta m/ Delta n = 1.05 and were only observed at sufficiently high NH sub(3) / H sub(2)SO sub(4). The H sub(2)SO sub(4) molecules of these clusters are partially neutralized by NH sub(3), in close resemblance to the acid-base bindings of ammonium bisulfate. Supported by model simulations, we substantiate previous evidence for acid-base reactions being the essential mechanism behind the formation of these clusters under atmospheric conditions and up to sizes of at least 2 nm. Our results also suggest that electrically neutral NH sub(3)-H sub(2)SO sub(4) clusters, unobservable in this study, have generally the same composition as ionic clusters for NH sub(3) / H sub(2)SO sub(4) > 10. We expect that NH sub(3)-H sub(2)SO sub(4) clusters form and grow also mostly by Delta m/ Delta n > 1 in the atmosphere's boundary layer, as NH sub(3) / H sub(2)SO sub(4) is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH sub(3)-H sub(2)SO sub(4) anion clusters during new-particle formation in the Finnish boreal forest. However, the exact role of NH sub(3)-H sub(2)SO sub(4) clusters in boundary layer particle formation remains to be resolved.
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.
We report comprehensive, demonstrably contaminant‐free measurements of binary particle formation rates by sulfuric acid and water for neutral and ion‐induced pathways conducted in the European ...Organization for Nuclear Research Cosmics Leaving Outdoor Droplets chamber. The recently developed Atmospheric Pressure interface‐time of flight‐mass spectrometer was used to detect contaminants in charged clusters and to identify runs free of any contaminants. Four parameters were varied to cover ambient conditions: sulfuric acid concentration (105 to 109 mol cm−3), relative humidity (11% to 58%), temperature (207 K to 299 K), and total ion concentration (0 to 6800 ions cm−3). Formation rates were directly measured with novel instruments at sizes close to the critical cluster size (mobility size of 1.3 nm to 3.2 nm). We compare our results with predictions from Classical Nucleation Theory normalized by Quantum Chemical calculation (QC‐normalized CNT), which is described in a companion paper. The formation rates predicted by the QC‐normalized CNT were extended from critical cluster sizes to measured sizes using the UHMA2 sectional particle microphysics model. Our results show, for the first time, good agreement between predicted and measured particle formation rates for the binary (neutral and ion‐induced) sulfuric acid‐water system. Formation rates increase with RH, sulfuric acid, and ion concentrations and decrease with temperature at fixed RH and sulfuric acid concentration. Under atmospheric conditions, neutral particle formation dominates at low temperatures, while ion‐induced particle formation dominates at higher temperatures. The good agreement between the theory and our comprehensive data set gives confidence in using the QC‐normalized CNT as a powerful tool to study neutral and ion‐induced binary particle formation in atmospheric modeling.
Key Points
Atmospheric binary particle formation can be both kinetic and nucleation type
Both ion‐induced and neutral pathways are strong at free‐tropospheric conditions
Ion‐induced pathway dominates at midtroposphere, neutral at upper troposphere
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.
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.
To study the effect of galactic cosmic rays on aerosols and clouds, the Cosmics Leaving OUtdoor Droplets (CLOUD) project was established. Experiments are carried out at a 26.1 m3 tank at CERN ...(Switzerland). In the experiments, the effect of ionizing radiation on H2SO4 particle formation and growth is investigated. To evaluate the experimental configuration, the experiment was simulated using a coupled multidimensional computational fluid dynamics (CFD) – particle model. In the model the coupled fields of gas/vapor species, temperature, flow velocity and particle properties were computed to investigate mixing state and mixing times of the CLOUD tank's contents. Simulation results show that a 1-fan configuration, as used in first experiments, may not be sufficient to ensure a homogeneously mixed chamber. To mix the tank properly, two fans and sufficiently high fan speeds are necessary. The 1/e response times for instantaneous changes of wall temperature and saturation ratio were found to be in the order of few minutes. Particle nucleation and growth was also simulated and particle number size distribution properties of the freshly nucleated particles (particle number, mean size, standard deviation of the assumed log-normal distribution) were found to be distributed over the tank's volume similar to the gas species.
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.
It has been claimed for more than a century that atmospheric new particle formation is primarily influenced by the presence of sulfuric acid. However, the activation process of sulfuric acid related ...clusters into detectable particles is still an unresolved topic. In this study we focus on the PARADE campaign measurements conducted during August/September 2011 at Mt Kleiner Feldberg in central Germany. During this campaign a set of radicals, organic and inorganic compounds and oxidants and aerosol properties were measured or calculated. We compared a range of organic and inorganic nucleation theories, evaluating their ability to simulate measured particle formation rates at 3 nm in diameter (J3) for a variety of different conditions. Nucleation mechanisms involving only sulfuric acid tentatively captured the observed noon-time daily maximum in J3, but displayed an increasing difference to J3 measurements during the rest of the diurnal cycle. Including large organic radicals, i.e. organic peroxy radicals (RO2) deriving from monoterpenes and their oxidation products, in the nucleation mechanism improved the correlation between observed and simulated J3. This supports a recently proposed empirical relationship for new particle formation that has been used in global models. However, the best match between theory and measurements for the site of interest was found for an activation process based on large organic peroxy radicals and stabilised Criegee intermediates (sCI). This novel laboratory-derived algorithm simulated the daily pattern and intensity of J3 observed in the ambient data. In this algorithm organic derived radicals are involved in activation and growth and link the formation rate of smallest aerosol particles with OH during daytime and NO3 during night-time. Because the RO2 lifetime is controlled by HO2 and NO we conclude that peroxy radicals and NO seem to play an important role for ambient radical chemistry not only with respect to oxidation capacity but also for the activation process of new particle formation. This is supposed to have significant impact of atmospheric radical species on aerosol chemistry and should be taken into account when studying the impact of new particles in climate feedback cycles.
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