Multicomponent new particle formation from sulfuric acid, ammonia, and biogenic vapors.
Ontology highlight
ABSTRACT:
SUBMITTER: Lehtipalo K
PROVIDER: S-EPMC6291317 | biostudies-literature | 2018 Dec
REPOSITORIES: biostudies-literature
Publications
Multicomponent new particle formation from sulfuric acid, ammonia, and biogenic vapors.
Lehtipalo Katrianne K Yan Chao C Dada Lubna L Bianchi Federico F Bianchi Federico F Xiao Mao M Wagner Robert R Stolzenburg Dominik D Ahonen Lauri R LR Amorim Antonio A Baccarini Andrea A Bauer Paulus S PS Baumgartner Bernhard B Bergen Anton A Bernhammer Anne-Kathrin AK Breitenlechner Martin M Brilke Sophia S Buchholz Angela A Mazon Stephany Buenrostro SB Chen Dexian D Chen Xuemeng X Dias Antonio A Dommen Josef J Draper Danielle C DC Duplissy Jonathan J Ehn Mikael M Finkenzeller Henning H Fischer Lukas L Frege Carla C Fuchs Claudia C Garmash Olga O Gordon Hamish H Hakala Jani J He Xucheng X Heikkinen Liine L Heinritzi Martin M Helm Johanna C JC Hofbauer Victoria V Hoyle Christopher R CR Jokinen Tuija T Kangasluoma Juha J Kerminen Veli-Matti VM Kim Changhyuk C Kirkby Jasper J Kontkanen Jenni J Kürten Andreas A Lawler Michael J MJ Mai Huajun H Mathot Serge S Mauldin Roy L RL Molteni Ugo U Nichman Leonid L Nie Wei W Nieminen Tuomo T Ojdanic Andrea A Onnela Antti A Passananti Monica M Petäjä Tuukka T Piel Felix F Pospisilova Veronika V Quéléver Lauriane L J LLJ Rissanen Matti P MP Rose Clémence C Sarnela Nina N Schallhart Simon S Schuchmann Simone S Sengupta Kamalika K Simon Mario M Sipilä Mikko M Tauber Christian C Tomé António A Tröstl Jasmin J Väisänen Olli O Vogel Alexander L AL Volkamer Rainer R Wagner Andrea C AC Wang Mingyi M Weitz Lena L Wimmer Daniela D Ye Penglin P Ylisirniö Arttu A Zha Qiaozhi Q Carslaw Kenneth S KS Curtius Joachim J Donahue Neil M NM Flagan Richard C RC Hansel Armin A Riipinen Ilona I Virtanen Annele A Winkler Paul M PM Baltensperger Urs U Kulmala Markku M Worsnop Douglas R DR
Science advances 20181212 12
A major fraction of atmospheric aerosol particles, which affect both air quality and climate, form from gaseous precursors in the atmosphere. Highly oxygenated organic molecules (HOMs), formed by oxidation of biogenic volatile organic compounds, are known to participate in particle formation and growth. However, it is not well understood how they interact with atmospheric pollutants, such as nitrogen oxides (NO <sub><i>x</i></sub> ) and sulfur oxides (SO <sub><i>x</i></sub> ) from fossil fuel co ...[more]
Similar Datasets
Project description: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 107 molecules cm-3, 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.
| S-EPMC6261657 | biostudies-literature
Project description:Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.
| S-EPMC3808659 | biostudies-literature
Project description:The magnitude of aerosol radiative forcing caused by anthropogenic emissions depends on the baseline state of the atmosphere under pristine preindustrial conditions. Measurements show that particle formation in atmospheric conditions can occur solely from biogenic vapors. Here, we evaluate the potential effect of this source of particles on preindustrial cloud condensation nuclei (CCN) concentrations and aerosol-cloud radiative forcing over the industrial period. Model simulations show that the pure biogenic particle formation mechanism has a much larger relative effect on CCN concentrations in the preindustrial atmosphere than in the present atmosphere because of the lower aerosol concentrations. Consequently, preindustrial cloud albedo is increased more than under present day conditions, and therefore the cooling forcing of anthropogenic aerosols is reduced. The mechanism increases CCN concentrations by 20-100% over a large fraction of the preindustrial lower atmosphere, and the magnitude of annual global mean radiative forcing caused by changes of cloud albedo since 1750 is reduced by [Formula: see text] (27%) to [Formula: see text] Model uncertainties, relatively slow formation rates, and limited available ambient measurements make it difficult to establish the significance of a mechanism that has its dominant effect under preindustrial conditions. Our simulations predict more particle formation in the Amazon than is observed. However, the first observation of pure organic nucleation has now been reported for the free troposphere. Given the potentially significant effect on anthropogenic forcing, effort should be made to better understand such naturally driven aerosol processes.
| S-EPMC5087035 | biostudies-literature
Project description:Organic interfaces that exist at the sea surface microlayer or as surfactant coatings on cloud droplets are highly concentrated and chemically distinct from the underlying bulk or overlying gas phase. Therefore, they may be potentially unique locations for chemical or photochemical reactions. Recently, photochemical production of volatile organic compounds (VOCs) was reported at a nonanoic acid interface however, subsequent secondary organic aerosol (SOA) particle production was incapable of being observed. We investigated SOA particle formation due to photochemical reactions occurring at an air-water interface in presence of model saturated long chain fatty acid and alcohol surfactants, nonanoic acid and nonanol, respectively. Ozonolysis of the gas phase photochemical products in the dark or under continued UV irradiation both resulted in nucleation and growth of SOA particles. Irradiation of nonanol did not yield detectable VOC or SOA production. Organic carbon functionalities of the SOA were probed using X-ray microspectroscopy and compared with other laboratory generated and field collected particles. Carbon-carbon double bonds were identified in the condensed phase which survived ozonolysis during new particle formation and growth. The implications of photochemical processes occurring at organic coated surfaces are discussed in the context of marine SOA particle atmospheric fluxes.
| S-EPMC5627235 | biostudies-literature
Project description:We recently coined the term clusteromics as a holistic approach for obtaining insight into the chemical complexity of atmospheric molecular cluster formation and at the same time providing the foundation for thermochemical databases that can be utilized for developing machine learning models. Here, we present the first paper in the series that applies state-of-the-art computational methods to study multicomponent (SA)0-2(base)0-2 clusters, with SA = sulfuric acid and base = [ammonia (A), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylenediamine (EDA)] with all combinations of the five bases. The initial cluster configurations are obtained using the ABCluster program and the number of relevant configurations are reduced based on PM7 and ωB97X-D/6-31++G(d,p) calculations. Thermochemical parameters are calculated based on the ωB97X-D/6-31++G(d,p) cluster structures and vibrational frequencies using the quasi-harmonic approximation. The single-point energies are refined with a high-level DLPNO-CCSD(T0)/aug-cc-pVTZ calculation. Using the calculated thermochemical data, we perform kinetics simulations to evaluate the potential of these small (SA)0-2(base)0-2 clusters to grow into larger cluster sizes. In all cases we find that having more than one type of base molecule present in the cluster will increase the potential for forming larger clusters primarily due to the increased available vapor concentration.
| S-EPMC7992168 | biostudies-literature
Project description:The excess of orbital detection of smectite deposits compared to carbonate deposits on the martian surface presents an enigma because smectite and carbonate formations are both favored alteration products of basalt under neutral to alkaline conditions. We propose that Mars experienced acidic events caused by sulfuric acid (H2SO4) that permitted phyllosilicate, but inhibited carbonate, formation. To experimentally verify this hypothesis, we report the first synthesis of smectite from Mars-analogue glass-rich basalt simulant (66 wt% glass, 32 wt% olivine, 2 wt% chromite) in the presence of H2SO4 under hydrothermal conditions (~200 °C). Smectites were analyzed by X-ray diffraction, Mossbauer spectroscopy, visible and near-infrared reflectance spectroscopy and electron microprobe to characterize mineralogy and chemical composition. Solution chemistry was determined by Inductively Coupled Plasma Mass Spectrometry. Basalt simulant suspensions in 11-42 mM H2SO4 were acidic with pH ≤ 2 at the beginning of incubation and varied from acidic (pH 1.8) to mildly alkaline (pH 8.4) at the end of incubation. Alteration of glass phase during reaction of the basalt simulant with H2SO4 led to formation of the dioctahedral smectite at final pH ~3 and trioctahedral smectite saponite at final pH ~4 and higher. Anhydrite and hematite formed in the final pH range from 1.8 to 8.4 while natroalunite was detected at pH 1.8. Hematite was precipitated as a result of oxidative dissolution of olivine present in Adirondack basalt simulant. Formation of secondary phases, including smectite, resulted in release of variable amounts of Si, Mg, Na and Ca while solubilization of Al and Fe was low. Comparison of mineralogical and solution chemistry data indicated that the type of smectite (i.e., dioctahedral vs trioctahedral) was likely controlled by Mg leaching from altering basalt and substantial Mg loss created favorable conditions for formation of dioctahedral smectite. We present a model for global-scale smectite formation on Mars via acid-sulfate conditions created by the volcanic outgassing of SO2 in the Noachian and early Hesperian.
| S-EPMC7427815 | biostudies-literature
Project description:For atmospheric sulfuric acid (SA) concentrations the presence of dimethylamine (DMA) at mixing ratios of several parts per trillion by volume can explain observed boundary layer new particle formation rates. However, the concentration and molecular composition of the neutral (uncharged) clusters have not been reported so far due to the lack of suitable instrumentation. Here we report on experiments from the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research revealing the formation of neutral particles containing up to 14 SA and 16 DMA molecules, corresponding to a mobility diameter of about 2 nm, under atmospherically relevant conditions. These measurements bridge the gap between the molecular and particle perspectives of nucleation, revealing the fundamental processes involved in particle formation and growth. The neutral clusters are found to form at or close to the kinetic limit where particle formation is limited only by the collision rate of SA molecules. Even though the neutral particles are stable against evaporation from the SA dimer onward, the formation rates of particles at 1.7-nm size, which contain about 10 SA molecules, are up to 4 orders of magnitude smaller compared with those of the dimer due to coagulation and wall loss of particles before they reach 1.7 nm in diameter. This demonstrates that neither the atmospheric particle formation rate nor its dependence on SA can simply be interpreted in terms of cluster evaporation or the molecular composition of a critical nucleus.
| S-EPMC4210346 | biostudies-literature
Project description:Rising air pollution levels in South Asia will have worldwide environmental consequences. Transport of pollutants from the densely populated regions of India, Pakistan, China, and Nepal to the Himalayas may lead to substantial radiative forcing in South Asia with potential effects on the monsoon circulation and, hence, on regional climate and hydrological cycles, as well as to dramatic impacts on glacier retreat. An improved description of particulate sources is needed to constrain the simulation of future regional climate changes. Here, the first evidence of very frequent new particle formation events occurring up to high altitudes is presented. A 16-month record of aerosol size distribution from the Nepal Climate Observatory at Pyramid (Nepal, 5,079 m above sea level), the highest atmospheric research station, is shown. Aerosol concentrations are driven by intense ultrafine particle events occurring on >35% of the days at the interface between clean tropospheric air and the more polluted air rising from the valleys. During a pilot study, we observed a significant increase of ion cluster concentrations with the onset of new particle formation events. The ion clusters rapidly grew to a 10-nm size within a few hours, confirming, thus, that in situ nucleation takes place up to high altitudes. The initiation of the new particle events coincides with the shift from free tropospheric downslope winds to thermal upslope winds from the valley in the morning hours. The new particle formation events represent a very significant additional source of particles possibly injected into the free troposphere by thermal winds.
| S-EPMC2566992 | biostudies-literature
Project description:Understanding new particle formation and their subsequent growth in the troposphere has a critical impact on our ability to predict atmospheric composition and global climate change. High pre-existing particle loadings have been thought to suppress the formation of new atmospheric aerosol particles due to high condensation and coagulation sinks. Here, based on field measurements at a mountain site in South China, we report, for the first time, in situ observational evidence on new particle formation and growth in remote ambient atmosphere during heavy dust episodes mixed with anthropogenic pollution. Both the formation and growth rates of particles in the diameter range 15-50 nm were enhanced during the dust episodes, indicating the influence of photo-induced, dust surface-mediated reactions and resulting condensable vapor production. This study provides unique in situ observations of heterogeneous photochemical processes inducing new particle formation and growth in the real atmosphere, and suggests an unexpected impact of mineral dust on climate and atmospheric chemistry.
| S-EPMC4198867 | biostudies-literature
Project description:Models that accurately predict atmospheric composition and correctly respond to tested policy scenarios aid air quality managers in the development of effective strategies to protect human health. Controllable emissions from human activity interact with natural emissions from plants and trees from the biosphere through complex chemistry to form ozone (O3) and organic fine particulate matter (PM2.5), criteria air pollutants that induce a variety of adverse health effects. While organic gases emitted from plants and trees are natural, some fraction of the subsequent O3 and PM2.5 is not. Accurate assessment of the extent to which human activity and natural emissions interact to form pollution can be achieved when models are constructed from first principle chemical and physical laws, and tested and evaluated with laboratory and field observations. In the summer of 2013, hundreds of scientists descended on the southeast U.S. to coordinate an atmospheric chemistry campaign with the ultimate goal of understanding complex biosphere-atmosphere interactions, the subsequent formation of O3 and PM2.5, and accurate incorporation of the chemistry into atmospheric models. A main finding from the campaign is that anthropogenic emissions facilitate formation of organic PM2.5 derived from biogenic VOCs. This fraction of PM2.5 is controllable pollution. Mechanistic insight from that campaign was recently incorporated into EPA's air quality model, improving the model representation of the atmospheric modeling and informing air quality management strategies for PM2.5. Emission reductions in SO2 and NOx in the southeast U.S. are found to reduce non-fossil, presumably biogenic, organic PM2.5 mass concentrations, suggesting existing Federal rules have been more successful than anticipated. Additional potential feedback mechanisms may become important as emissions reductions bring the atmosphere into new chemical regimes.
| S-EPMC7008308 | biostudies-literature