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.
A new particle size magnifier (PSM) for detection of nano-CN as small as ∼1 nm in mobility diameter was developed, calibrated and tested in atmospheric measurements. The working principle of a PSM is ...to mix turbulently cooled sample flow with heated clean air flow saturated by the working fluid. This provides a high saturation ratio for the working fluid and activates the seed particles and grows them by condensation of the working fluid. In order to reach high saturation ratios, and thus to activate nano-CN without homogeneous nucleation, diethylene glycol was chosen as the working fluid. The PSM was able to grow nano-CN to mean diameter of 90 nm, after which an ordinary condensation particle counter was used to count the grown particles (TSI 3010). The stability of the PSM was found to be good making it suitable for stand-alone field measurements. Calibration results show that the detection efficiency of the prototype PSM + TSI 3010 for charged tetra-alkyl ammonium salt molecules having mobility equivalent diameters of 1.05, 1.47, 1.78, and 2.57 nm are 25, 32, 46, and 70%, respectively. The commercial version of the PSM (Airmodus A09) performed even better in the smallest sizes the detection efficiency being 51% for 1.47 nm and 67% for 1.78 nm.
This review is based on ca. 260 publications, 93 of which included data on the temporal and spatial variation of the concentration of small ions (<1.6 nm in diameter) especially in the lower ...troposphere, chemical composition, or formation and growth rates of sub-3 nm ions. This information was collected on tables and figures. The small ions exist all the time in the atmosphere, and the average concentrations of positive and negative small ions are typically 200–2500 cm−3. However, concentrations up to 5000 cm−3 have been observed. The results are in agreement with observations of ion production rates in the atmosphere. We also summarised observations on the conversion of small ions to intermediate ions, which can act as embryos for new atmospheric aerosol particles. Those observations include the formation rates (J2ion) of 2-nm intermediate ions, growth rates (GRion) of sub-3 nm ions, and information on the chemical composition of the ions. Unfortunately, there were only a few studies which presented J2ion and GRion. Based on the publications, the formation rates of 2-nm ions were 0–1.1 cm−3 s−1, while the total 2-nm particle formation rates varied between 0.001 and 60 cm−3 s−1. Due to small changes in J2ion, the relative importance of ions in 2-nm particle formation was determined by the large changes in J2tot, and, accordingly the contribution of ions increased with decreasing J2tot. Furthermore, small ions were observed to activate for growth earlier than neutral nanometer-sized particles and at lower saturation ratio of condensing vapours.
A recently developed atmospheric pressure interface mass spectrometer (APi-TOF) measured the negative and positive ambient ion composition at a boreal forest site. As observed in previous studies, ...the negative ions were dominated by strong organic and inorganic acids (e.g. malonic, nitric and sulfuric acid), whereas the positive ions consisted of strong bases (e.g. alkyl pyridines and quinolines). Several new ions and clusters of ions were identified based on their exact masses, made possible by the high resolution, mass accuracy and sensitivity of the APi-TOF. Time series correlograms aided in peak identification and assigning the atomic compositions to molecules. Quantum chemical calculations of proton affinities and cluster stabilities were also used to confirm the plausibility of the assignments. Acids in the gas phase are predominantly formed by oxidation in the gas phase, and thus the concentrations are expected to vary strongly between day and night. This was also the case in this study, where the negative ions showed strong diurnal behavior, whereas the daily changes in the positive ions were considerably smaller. A special focus in this work was the changes in the ion distributions occurring during new particle formation events. We found that sulfuric acid, together with its clusters, dominated the negative ion spectrum during these events. The monomer (HSO4−) was the largest peak, together with the dimer (H2SO4 · HSO4−) and trimer ((H2SO4)2 · HSO4−). SO5− also tracked HSO4− at around 20% of the HSO4− concentration at all times. During the strongest events, the tetramer and a cluster with the tetramer and ammonia were also detected. Quantum chemical calculations predict that sulfuric acid clusters containing ammonia are much more stable when neutral, thus the detection of a single ion cluster implies that ammonia can be an important compound in the nucleation process. We also believe to have made the first observations of an organosulfate (glycolic acid sulfate) in the gas phase. This ion, and its cluster with sulfuric acid, correlates with the HSO4−, but peaks in the early afternoon, some hours later than HSO4− itself. A list of all identified ions is presented in the supplementary material, and also a list of all detected masses not yet identified.
Sulphuric acid and organic vapours have been identified as the key components in the ubiquitous secondary new particle formation in the atmosphere. In order to assess their relative contribution and ...spatial variability, we analysed altogether 36 new particle formation events observed at four European measurement sites during EUCAARI campaigns in 2007-2009. We tested models of several different nucleation mechanisms coupling the formation rate of neutral particles (J) with the concentration of sulphuric acid (H2 SO4 ) or low-volatility organic vapours (org) condensing on sub-4 nm particles, or with a combination of both concentrations. Furthermore, we determined the related nucleation coefficients connecting the neutral nucleation rate J with the vapour concentrations in each mechanism. The main goal of the study was to identify the mechanism of new particle formation and subsequent growth that minimizes the difference between the modelled and measured nucleation rates. At three out of four measurement sites - Hyytiälä (Finland), Melpitz (Germany) and San Pietro Capofiume (Italy) - the nucleation rate was closely connected to squared sulphuric acid concentration, whereas in Hohenpeissenberg (Germany) the low-volatility organic vapours were observed to be dominant. However, the nucleation rate at the sulphuric acid dominant sites could not be described with sulphuric acid concentration and a single value of the nucleation coefficient, as K in J=K H2 SO4 2 , but the median coefficients for different sites varied over an order of magnitude. This inter-site variation was substantially smaller when the heteromolecular homogenous nucleation between H2 SO4 and organic vapours was assumed to take place in addition to homogenous nucleation of H2 SO4 alone, i.e., J=KSA1 H2 SO4 2 +KSA2 H2 SO4 org. By adding in this equation a term describing homomolecular organic vapour nucleation, Ks3 org2 , equally good results were achieved. In general, our results suggest that organic vapours do play a role, not only in the condensational growth of the particles, but also in the nucleation process, with a site-specific degree.
New insights into nocturnal nucleation Ortega, I. K; Suni, T; Boy, M ...
Atmospheric chemistry and physics,
05/2012, Letnik:
12, Številka:
9
Journal Article
Recenzirano
Odprti dostop
Formation of new aerosol particles by nucleation and growth is a significant source of aerosols in the atmosphere. New particle formation events usually take place during daytime, but in some ...locations they have been observed also at night. In the present study we have combined chamber experiments, quantum chemical calculations and aerosol dynamics models to study nocturnal new particle formation. All our approaches demonstrate, in a consistent manner, that the oxidation products of monoterpenes play an important role in nocturnal nucleation events. By varying the conditions in our chamber experiments, we were able to reproduce the very different types of nocturnal events observed earlier in the atmosphere. The exact strength, duration and shape of the events appears to be sensitive to the type and concentration of reacting monoterpenes, as well as the extent to which the monoterpenes are exposed to ozone and potentially other atmospheric oxidants.
The Antarctic near-coastal sub-micrometre aerosol particle features in summer were characterised based on measured data on aerosol hygroscopicity, size distributions, volatility and chemical ion and ...organic carbon mass concentrations. Hysplit model was used to calculate the history of the air masses to predict the particle origin. Additional measurements of meteorological parameters were utilised. The hygroscopic properties of particles mostly resembled those of marine aerosols. The measurements took place at 130 km from the Southern Ocean, which was the most significant factor affecting the particle properties. This is explained by the lack of additional sources on the continent of Antarctica. The Southern Ocean was thus a likely source of the particles and nucleating and condensing vapours. The particles were very hygroscopic (HGF 1.75 at 90 nm) and very volatile. Most of the sub-100 nm particle volume volatilised below 100 °C. Based on chemical data, particle hygroscopic and volatile properties were explained by a large fraction of non-neutralised sulphuric acid together with organic material. The hygroscopic growth factors assessed from chemical data were similar to measured. Hygroscopicity was higher in dry continental air masses compared with the moist marine air masses. This was explained by the aging of the marine organic species and lower methanesulphonic acid volume fraction together with the changes in the inorganic aerosol chemistry as the aerosol had travelled long time over the continental Antarctica. Special focus was directed in detailed examination of the observed new particle formation events. Indications of the preference of negative over positive ions in nucleation could be detected. However, in a detailed case study, the neutral particles dominated the particle formation process. Freshly nucleated particles had the smallest hygroscopic growth factors, which increased subsequent to particle aging.
While cloud condensation nuclei (CCN) production associated with atmospheric new particle formation (NPF) is thought to be frequent throughout the continental boundary layers, few studies on this ...phenomenon in marine air exist. Here, based on simultaneous measurement of particle number size distributions, CCN properties and aerosol chemical composition, we present the first direct evidence on CCN production resulting from NPF in the eastern Mediterranean atmosphere. We show that condensation of both gaseous sulfuric acid and organic compounds from multiple sources leads to the rapid growth of nucleated particles to CCN sizes in this environment during the summertime. Sub-100 nm particles were found to be substantially less hygroscopic than larger particles during the period with active NPF and growth (the value of κ was lower by 0.2–0.4 for 60 nm particles compared with 120 nm particles), probably due to enrichment of organic material in the sub-100 nm size range. The aerosol hygroscopicity tended to be at minimum just before the noon and at maximum in the afternoon, which was very likely due to the higher sulfate-to-organic ratios and higher degree of oxidation of the organic material during the afternoon. Simultaneous with the formation of new particles during daytime, particles formed during the previous day or even earlier were growing into the size range relevant to cloud droplet activation, and the particles formed in the atmosphere were possibly mixed with long-range-transported particles.
South Africa holds significant mineral resources, with a substantial fraction of these reserves occurring and being processed in a large geological structure termed the Bushveld Igneous Complex ...(BIC). The area is also highly populated by informal, semi-formal and formal residential developments. However, knowledge of air quality and research related to the atmosphere is still very limited in the area. In order to investigate the characteristics and processes affecting sub-micron particle number concentrations and formation events, air ion and aerosol particle size distributions and number concentrations, together with meteorological parameters, trace gases and particulate matter (PM) were measured for over two years at Marikana in the heart of the western BIC. The observations showed that trace gas (i.e. SO2, NOx, CO) and black carbon concentrations were relatively high, but in general within the limits of local air quality standards. The area was characterised by very high condensation sink due to background aerosol particles, PM10 and O3 concentration. The results indicated that high amounts of Aitken and accumulation mode particles originated from domestic burning for heating and cooking in the morning and evening, while during daytime SO2-based nucleation followed by the growth by condensation of vapours from industrial, residential and natural sources was the most probable source for large number concentrations of nucleation and Aitken mode particles. Nucleation event day frequency was extremely high, i.e. 86% of the analysed days, which to the knowledge of the authors is the highest frequency ever reported. The air mass back trajectory and wind direction analyses showed that the secondary particle formation was influenced both by local and regional pollution and vapour sources. Therefore, our observation of the annual cycle and magnitude of the particle formation and growth rates during nucleation events were similar to results previously published for a semi-clean savannah site in South Africa.
Formation of new aerosol particles from trace gases is a major source of cloud condensation nuclei (CCN) in the global atmosphere, with potentially large effects on cloud optical properties and ...Earth's radiative balance. Controlled laboratory experiments have resolved, in detail, the different nucleation pathways likely responsible for atmospheric new particle formation, yet very little is known from field studies about the molecular steps and compounds involved in different regions of the atmosphere. The scarcity of primary particle sources makes secondary aerosol formation particularly important in the Antarctic atmosphere. Here, we report on the observation of ion-induced nucleation of sulfuric acid and ammonia-a process experimentally investigated by the CERN CLOUD experiment-as a major source of secondary aerosol particles over coastal Antarctica. We further show that measured high sulfuric acid concentrations, exceeding 10
molecules cm
, are sufficient to explain the observed new particle growth rates. Our findings show that ion-induced nucleation is the dominant particle formation mechanism, implying that galactic cosmic radiation plays a key role in new particle formation in the pristine Antarctic atmosphere.
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