On the roles of sulphuric acid and low-volatility organic vapours in  the initial steps of atmospheric new particle formation

Paasonen, Pauli; Nieminen, Tuomo; Asmi, Eija; Manninen, Hanna E.; Petäj̈ä, Tuukka; Plaß-Dülmer, C.; Flentje, H.; Birmili, W.; Wiedensohler, Alfred; Hõrrak, Urmas; Metzger, Axel; Hamed, A.; Laaksonen, A.; Facchini, M. C.; Kerminen, V.-M.; Kulmala, Markku

doi:10.5194/acp-10-11223-2010

Cited by 282 publications

(362 citation statements)

References 63 publications

(83 reference statements)

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“…Recent laboratory experiments have shown the importance of sulfuric acid and low-volatile oxidized organic vapors to NPF Kirkby et al, 2011;Petäjä et al, 2011;Kulmala et al, 2013;Ehn et al, 2014;Riccobono et al, 2014). Additionally, atmospheric observations confirm the importance of these precursor vapors in the initial steps of NPF and in the further growth of newly formed particles (Kulmala et al, 1998;Smith et al, 2005;Kerminen et al, 2010;Paasonen et al, 2010;Ahlm et al, 2012;Bzdek et al, 2014;Nieminen et al, 2014;Vakkari et al, 2015). The Station for Measuring Forest Ecosystem-Atmosphere Relations (SMEAR II), located in Hyytiälä, southern Finland, compiles almost 21 years of particle number size distribution and extensive complementary data, providing the longest size distribution time series in the world, and hence allows for robust NPF analysis which is not readily possible at other sites.…”

Section: Introductionmentioning

confidence: 73%

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Long-term analysis of clear-sky new particle formation events and nonevents in Hyytiälä

et al. 2017

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Abstract. New particle formation (NPF) events have been observed all around the world and are known to be a major source of atmospheric aerosol particles. Here we combine 20 years of observations in a boreal forest at the SMEAR II station (Station for Measuring Ecosystem-Atmosphere Relations) in Hyytiälä, Finland, by building on previously accumulated knowledge and by focusing on clear-sky (noncloudy) conditions. We first investigated the effect of cloudiness on NPF and then compared the NPF event and nonevent days during clear-sky conditions. In this comparison we considered, for example, the effects of calculated particle formation rates, condensation sink, trace gas concentrations and various meteorological quantities in discriminating NPF events from nonevents. The formation rate of 1.5 nm particles was calculated by using proxies for gaseous sulfuric acid and oxidized products of low volatile organic compounds, together with an empirical nucleation rate coefficient. As expected, our results indicate an increase in the frequency of NPF events under clear-sky conditions in comparison to cloudy ones. Also, focusing on clear-sky conditions enabled us to find a clear separation of many variables related to NPF. For instance, oxidized organic vapors showed a higher concentration during the clear-sky NPF event days, whereas the condensation sink (CS) and some trace gases had higher concentrations during the nonevent days. The calculated formation rate of 3 nm particles showed a notable difference between the NPF event and nonevent days during clear-sky conditions, especially in winter and spring. For springtime, we are able to find a threshold equation for the combined values of ambient temperature and CS, (CS (s −1 ) > −3.091 × 10 −5 × T (in Kelvin) + 0.0120), above which practically no clear-sky NPF event could be observed. Finally, we present a probability distribution for the frequency of NPF events at a specific CS and temperature.

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Section: Introductionmentioning

confidence: 73%

“…(5) is the median estimated coefficient for Hyytiälä scaled from Paasonen et al (2010): K het = 9.2 × 10 −14 cm 3 s −1 . The scaling was made in order to fit the current data.…”

Section: Particle Formation Ratesmentioning

confidence: 99%

Long-term analysis of clear-sky new particle formation events and nonevents in Hyytiälä

et al. 2017

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“…The agreement between the calculated condensable vapor concentration and calculated sulfuric acid concentrations during the nucleation process (3.67 AE 0.78× 10 þ07 molecules∕cm 3 in average) suggests that the nucleation events observed is likely linked to the H 2 SO 4 produced from the atmospheric oxidation of the volcanic emitted SO 2 . As a consequence, this observation may also indicate that condensable vapors different than sulfuric acid are not needed to explain the observed new particle growth, contrarily to what it is usually observed during nucleation and growth events in the planetary boundary layer under remote conditions (23). When particles grow above a certain limit, between 50 and 100 nm diameter, they can act as CCN.…”

Section: New Particle Formation Eventsmentioning

confidence: 88%

Observations of nucleation of new particles in a volcanic plume

Boulon

Sellegri

Hervo

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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Volcanic eruptions caused major weather and climatic changes on timescales ranging from hours to centuries in the past. Volcanic particles are injected in the atmosphere both as primary particles rapidly deposited due to their large sizes on time scales of minutes to a few weeks in the troposphere, and secondary particles mainly derived from the oxidation of sulfur dioxide. These particles are responsible for the atmospheric cooling observed at both regional and global scales following large volcanic eruptions. However, large condensational sinks due to preexisting particles within the plume, and unknown nucleation mechanisms under these circumstances make the assumption of new secondary particle formation still uncertain because the phenomenon has never been observed in a volcanic plume. In this work, we report the first observation of nucleation and new secondary particle formation events in a volcanic plume. These measurements were performed at the puy de Dôme atmospheric research station in central France during the Eyjafjallajokull volcano eruption in Spring 2010. We show that the nucleation is indeed linked to exceptionally high concentrations of sulfuric acid and present an unusual high particle formation rate. In addition we demonstrate that the binary H 2 SO 4 − H 2 O nucleation scheme, as it is usually considered in modeling studies, underestimates by 7 to 8 orders of magnitude the observed particle formation rate and, therefore, should not be applied in tropospheric conditions. These results may help to revisit all past simulations of the impact of volcanic eruptions on climate.secondary aerosols | volcanic sulfur | nanoparticles V olcanic eruptions and their impact on climate have been extensively investigated in geological archives such as sediments (1), ice cores (2-5), and through modeling studies (6, 7) but processes taking place in the volcanic plume have rarely been directly observed. The sulfur dioxide emitted in large amounts during explosive volcanic eruptions (8) can be oxidized to sulfuric acid, thus many authors suspect that the formed sulfuric acid gives rise to the formation of new secondary particle from binary homogeneous nucleation mechanism (1, 9-12). Those new particles can then affect the atmospheric radiative balance both directly and indirectly because they can act as cloud condensation nuclei (CCN) (13). This leads to a cooling effect, which is on a time scale from months to years, depending on the location of the eruption and the height at which volcanic gases were emitted.The Eyjafjallajokull volcano located in the south of Iceland [63°38′ N, 19°36′ W, summit 1,660 m above sea level (asl)] erupted on March 20, 2010. A major outbreak of the central crater under the covering ice cap followed on April 14, 2010 (Institute of Earth Sciences, 2010). A large volcanic plume composed of ashes and gases rose up to the tropopause level (approximately 10 km) for days and were observed by satellite and ground-based remote sensing instruments. The volcanic plume reached European altitude s...

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“…1). However, the latter reveal distinct regional differences, with some environments showing nucleation rates both above and below the amine limit (boreal forest and mountain 21,22 ), whereas others are only below the limit (agricultural, livestock, industrial and urban 21,23 ). This suggests that nucleation in different regions of the boundary layer may be controlled by different ternary vapours.…”

mentioning

confidence: 99%

Molecular understanding of sulphuric acid–amine particle nucleation in the atmosphere

Almeida

Schobesberger

Kürten

et al. 2013

Nature

841

1,107

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Nucleation of aerosol particles from trace atmospheric vapours is thought to provide up to half of global cloud condensation nuclei 1 . Aerosols can cause a net cooling of climate by scattering sunlight and by leading to smaller but more numerous cloud droplets, which makes clouds brighter and extends their lifetimes 2 . Atmospheric aerosols derived from human activities are thought to have compensated for a large fraction of the warming caused by greenhouse gases 2 . However, despite its importance for climate, atmospheric nucleation is poorly understood. Recently, it has been shown that sulphuric acid and ammonia cannot explain particle formation rates observed in the lower atmosphere 3 . It is thought that amines may enhance nucleation 4-16 , but until now there has been no direct evidence for amine ternary nucleation under atmospheric conditions. Here we use the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN and find that dimethylamine above three parts per trillion by volume can enhance particle formation rates more than 1,000-fold compared with ammonia, sufficient to account for the particle formation rates observed in the atmosphere. Molecular analysis of the clusters reveals that the faster nucleation is explained by a base-stabilization mechanism involving acid-amine pairs, which strongly decrease evaporation. The ion-induced contribution is generally small, reflecting the high stability of sulphuric acid-dimethylamine clusters and indicating that galactic cosmic rays exert only a small influence on their formation, except at low overall formation rates. Our experimental measurements are well reproduced by a dynamical model based on quantum chemical calculations of binding energies of molecular clusters, without any fitted parameters. These results show that, in regions of the atmosphere near amine sources, both amines and sulphur dioxide should be considered when assessing the impact of anthropogenic activities on particle formation.The primary vapour responsible for atmospheric nucleation is thought to be sulphuric acid (H 2 SO 4 ), derived from the oxidation of sulphur dioxide. However, peak daytime H 2 SO 4 concentrations in the atmospheric boundary layer are about 10 6 to 3 3 10 7 cm 23 (0.04-1.2 parts per trillion by volume (p.p.t.v.)), which results in negligible binary homogeneous nucleation of H 2 SO 4 -H 2 O (ref. 3). Additional species such as ammonia or amines 4,5 are therefore necessary to stabilize the embryonic clusters and decrease evaporation. However, ammonia cannot account for particle formation rates observed in the boundary layer 3 and, despite numerous field and laboratory studies [6][7][8][9][10][11][12][13][14][15][16] , amine ternary nucleation has not yet been observed under atmospheric conditions. Amine emissions are dominated by anthropogenic activities (mainly animal husbandry), but about 30% of emissions are thought to arise from the breakdown of organic matter in the oceans, and 20% from biomass burning and soil 8,17 . Atmospheric measurements of gasphase amines ...

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On the roles of sulphuric acid and low-volatility organic vapours in the initial steps of atmospheric new particle formation

Cited by 282 publications

References 63 publications

Long-term analysis of clear-sky new particle formation events and nonevents in Hyytiälä

Long-term analysis of clear-sky new particle formation events and nonevents in Hyytiälä

Observations of nucleation of new particles in a volcanic plume

Molecular understanding of sulphuric acid–amine particle nucleation in the atmosphere

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