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Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth
(2012)
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 formation and to the early growth of nucleated particles, respectively. 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 dominated by organic compounds already 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 particles growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. The size resolved growth analysis finally indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.
Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth
(2012)
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 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 (NH3) and sulfuric acid (H2SO4). 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 NH3–H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from < 2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm−3 (0.1 to 56 pptv), and a temperature range from −25 to +20 °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 NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, 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 NH3–H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O–H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4] < 0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3–H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm/Δ n), where n is in the range 4–18 (negatively charged clusters) or 1–17 (positively charged clusters). For negatively charged clusters, Δ m/Δn saturated between 1 and 1.4 for [NH3] / [H2SO4] > 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, 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 NH3–H2SO4 clusters, unobservable in this study, have generally the same composition as ionic clusters for [NH3] / [H2SO4] > 10. We expect that NH3–H2SO4 clusters form and grow also mostly by Δm/Δn > 1 in the atmosphere's boundary layer, as [NH3] / [H2SO4] is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH3–H2SO4 anion clusters during new-particle formation in the Finnish boreal forest. However, the exact role of NH3–H2SO4 clusters in boundary layer particle formation remains to be resolved.
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 (NH3) and sulfuric acid (H2SO4). 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 NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from <2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm−3, and a temperature range from −25 to +20 °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 NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, 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 NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4]<0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm / Δn), where n is in the range 4–18 (negatively charged clusters) or 1–17 (positively charged clusters). For negatively charged clusters, Δm / Δn saturated between 1 and 1.4 for [NH3] / [H2SO4]>10. Positively charged clusters grew on average by Δm / Δn = 1.05 and were only observed at sufficiently high [NH3] / [H2SO4]. The H2SO4 molecules of these clusters are partially neutralized by NH3, 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 yet unobservable electrically neutral NH3-H2SO4 clusters grow by generally the same mechanism as ionic clusters, particularly for [NH3] / [H2SO4]>10. We expect that NH3-H2SO4 clusters form and grow also mostly by Δm / Δn>1 in the atmosphere's boundary layer, as [NH3] / [H2SO4] is mostly larger than 10. We compared our results from CLOUD with APi-TOF measurements of NH3-H2SO4 anion clusters during new particle formation in the Finnish boreal forest. However, the exact role of NH3-H2SO4 clusters in boundary layer particle formation remains to be resolved.
The formation of secondary particles in the atmosphere accounts for more than half of global cloud condensation nuclei. Experiments at the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber have underlined the importance of ions for new particle formation, but quantifying their effect in the atmosphere remains challenging. By using a novel instrument setup consisting of two nano-particle counters, one of them equipped with an ion filter, we were able to further investigate the ion-related mechanisms of new particle formation. In autumn 2015, we carried out experiments at CLOUD on four systems of different chemical compositions involving monoterpenes, sulfuric acid, nitrogen oxides, and ammonia. We measured the influence of ions on the nucleation rates under precisely controlled and atmospherically relevant conditions. Our results indicate that ions enhance the nucleation process when the charge is necessary to stabilize newly formed clusters, i.e. in conditions where neutral clusters are unstable. For charged clusters that were formed by ion-induced nucleation, we were able to measure, for the first time, their progressive neutralization due to recombination with oppositely charged ions. A large fraction of the clusters carried a charge at 1.2 nm diameter. However, depending on particle growth rates and ion concentrations, charged clusters were largely neutralized by ion–ion recombination before they grew to 2.2 nm. At this size, more than 90 % of particles were neutral. In other words, particles may originate from ion-induced nucleation, although they are neutral upon detection at diameters larger than 2.2 nm. Observations at Hyytiälä, Finland, showed lower ion concentrations and a lower contribution of ion-induced nucleation than measured at CLOUD under similar conditions. Although this can be partly explained by the observation that ion-induced fractions decrease towards lower ion concentrations, further investigations are needed to resolve the origin of the discrepancy.