scholarly journals Semi-empirical parameterization of size-dependent atmospheric nanoparticle growth in continental environments

2013 ◽  
Vol 13 (15) ◽  
pp. 7665-7682 ◽  
Author(s):  
S. A. K. Häkkinen ◽  
H. E. Manninen ◽  
T. Yli-Juuti ◽  
J. Merikanto ◽  
M. K. Kajos ◽  
...  
Keyword(s):  
Large Scale ◽  
Cloud Condensation Nuclei ◽  
Anthropogenic Pollution ◽  
Particle Growth ◽  
Oxidation Products ◽  
Forest Site ◽  
Nanoparticle Growth ◽  
One Year ◽  
20 Nm ◽  
Semi Empirical

Abstract. The capability to accurately yet efficiently represent atmospheric nanoparticle growth by biogenic and anthropogenic secondary organics is a challenge for current atmospheric large-scale models. It is, however, crucial to predict nanoparticle growth accurately in order to reliably estimate the atmospheric cloud condensation nuclei (CCN) concentrations. In this work we introduce a simple semi-empirical parameterization for sub-20 nm particle growth that distributes secondary organics to the nanoparticles according to their size and is therefore able to reproduce particle growth observed in the atmosphere. The parameterization includes particle growth by sulfuric acid, secondary organics from monoterpene oxidation (SORGMT) and an additional condensable vapor of non-monoterpene organics ("background"). The performance of the proposed parameterization was investigated using ambient data on particle growth rates in three diameter ranges (1.5–3 nm, 3–7 nm and 7–20 nm). The growth rate data were acquired from particle/air ion number size distribution measurements at six continental sites over Europe. The longest time series of 7 yr (2003–2009) was obtained from a boreal forest site in Hyytiälä, Finland, while about one year of data (2008–2009) was used for the other stations. The extensive ambient measurements made it possible to test how well the parameterization captures the seasonal cycle observed in sub-20 nm particle growth and to determine the weighing factors for distributing the SORGMT for different sized particles as well as the background mass flux (concentration). Besides the monoterpene oxidation products, background organics with a concentration comparable to SORGMT, around 6 × 107 cm−3 (consistent with an additional global SOA yield of 100 Tg yr−1) was needed to reproduce the observed nanoparticle growth. Simulations with global models suggest that the "background" could be linked to secondary biogenic organics that are formed in the presence of anthropogenic pollution.

scholarly journals Semi-empirical parameterization of size-dependent atmospheric nanoparticle growth in continental environments

2013 ◽  
Vol 13 (3) ◽  
pp. 8489-8535 ◽  
Author(s):  
S. A. K. Häkkinen ◽  
H. E. Manninen ◽  
T. Yli-Juuti ◽  
J. Merikanto ◽  
M. K. Kajos ◽  
...  
Keyword(s):  
Large Scale ◽  
Cloud Condensation Nuclei ◽  
Anthropogenic Pollution ◽  
Particle Growth ◽  
Oxidation Products ◽  
Forest Site ◽  
Nanoparticle Growth ◽  
One Year ◽  
20 Nm ◽  
Semi Empirical

Abstract. The capability to accurately yet efficiently represent atmospheric nanoparticle growth by biogenic and anthropogenic secondary organics is a challenge for current atmospheric large-scale models. It is, however, crucial to predict nanoparticle growth accurately in order to reliably estimate the atmospheric cloud condensation nuclei (CCN) concentrations. In this work we introduce a~simple semi-empirical parameterization for sub-20 nm particle growth that distributes secondary organics to the nanoparticles according to their size and is therefore able to reproduce particle growth observed in the atmosphere. The parameterization includes particle growth by sulfuric acid, secondary organics from monoterpene oxidation (SORGMT) and an additional condensable non-monoterpene organics ("background"). The performance of the proposed parameterization was investigated using ambient data on particle growth rates in three size ranges (1.5–3 nm, 3–7 nm and 7–20 nm). The growth rate data was acquired from particle/air ion number size distribution measurements at six continental sites over Europe. The longest time series of 7 yr (2003 to 2009) was obtained from a boreal forest site in Hyytiälä, Finland, while about one year of data (2008–2009) was used for the other stations. The extensive ambient measurements made it possible to test how well the parameterization captures the seasonal cycle observed in sub-20 nm particle growth and to determine the weighing factors for distributing the SORGMT for different sized particles as well as the background mass flux (/concentration). Besides the monoterpene oxidation products, background organics with a concentration comparable to SORGMT, around 6 × 107 cm−3 (consistent with an additional global SOA yield of 100 Tg yr−1) was needed to reproduce the observed nanoparticle growth. Simulations with global models suggest that the "background" could be linked to secondary biogenic organics that are formed in the presence of anthropogenic pollution.

scholarly journals Parameterization of ion-induced nucleation rates based on ambient observations

2010 ◽  
Vol 10 (9) ◽  
pp. 21697-21720 ◽  
Author(s):  
T. Nieminen ◽  
P. Paasonen ◽  
H. E. Manninen ◽  
V.-M. Kerminen ◽  
M. Kulmala
Keyword(s):  
Large Scale ◽  
Formation Rate ◽  
Global Radiation ◽  
Atmospheric Models ◽  
Organic Vapor ◽  
Depth Analysis ◽  
Using Data ◽  
One Year ◽  
Project Data ◽  
Semi Empirical

Abstract. Atmospheric ions participate in the formation of new atmospheric aerosol particles, yet their exact role in this process has remained unclear. Here we derive a new simple parameterization for ion-induced nucleation or, more precisely, for the formation rate of charged 2-nm particles. The parameterization is semi-empirical in the sense that it is based on comprehensive results of one-year-long atmospheric cluster and particle measurements in the size range ∼1–42 nm within the EUCAARI (European Integrated project on Aerosol Cloud Climate and Air Quality interactions) project. Data from 12 field sites across Europe measured with different types of air ion and cluster mobility spectrometers were used in our analysis, with more in-depth analysis made using data from four stations with concomitant sulphuric acid measurements. The parameterization was given in two slightly different forms: a more accurate one that requires information on sulfuric acid and nucleating organic vapor concentrations, and a simpler one in which this information is replaced with the global radiation intensity. In principle, these new parameterizations are applicable to all large-scale atmospheric models containing size-resolved aerosol microphysics.

scholarly journals A chamber study of the influence of boreal BVOC emissions and sulfuric acid on nanoparticle formation rates at ambient concentrations

2016 ◽  
Vol 16 (4) ◽  
pp. 1955-1970 ◽  
Author(s):  
M. Dal Maso ◽  
L. Liao ◽  
J. Wildt ◽  
A. Kiendler-Scharr ◽  
E. Kleist ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Cloud Condensation Nuclei ◽  
Formation Rate ◽  
Particle Growth ◽  
Oxidation Products ◽  
Aerosol Formation ◽  
Nanoparticle Formation ◽  
Aerosol Nanoparticles ◽  
Chamber Study ◽  
Ambient Concentrations

Abstract. Aerosol formation from biogenic and anthropogenic precursor trace gases in continental background areas affects climate via altering the amount of available cloud condensation nuclei. Significant uncertainty still exists regarding the agents controlling the formation of aerosol nanoparticles. We have performed experiments in the Jülich plant–atmosphere simulation chamber with instrumentation for the detection of sulfuric acid and nanoparticles, and present the first simultaneous chamber observations of nanoparticles, sulfuric acid, and realistic levels and mixtures of biogenic volatile compounds (BVOCs). We present direct laboratory observations of nanoparticle formation from sulfuric acid and realistic BVOC precursor vapour mixtures performed at atmospherically relevant concentration levels. We directly measured particle formation rates separately from particle growth rates. From this, we established that in our experiments, the formation rate was proportional to the product of sulfuric acid and biogenic VOC emission strength. The formation rates were consistent with a mechanism in which nucleating BVOC oxidation products are rapidly formed and activate with sulfuric acid. The growth rate of nanoparticles immediately after birth was best correlated with estimated products resulting from BVOC ozonolysis.

scholarly journals Probing key organic substances driving new particle growth initiated by iodine nucleation in coastal atmosphere

2020 ◽  
Vol 20 (16) ◽  
pp. 9821-9835
Author(s):  
Yibei Wan ◽  
Xiangpeng Huang ◽  
Bin Jiang ◽  
Binyu Kuang ◽  
Manfei Lin ◽  
...  
Keyword(s):  
Organic Compounds ◽  
Unsaturated Fatty Acids ◽  
Cloud Condensation Nuclei ◽  
Deep Understanding ◽  
Surface Group ◽  
Particle Growth ◽  
Biologically Active ◽  
Ion Cyclotron Resonance ◽  
20 Nm ◽  
Ft Icr Ms

Abstract. Unlike the deep understanding of highly oxygenated organic molecules (HOMs) driving continental new particle formation (NPF), little is known about the organic compounds involved in coastal and open-ocean NPF. On the coastline of China we observed intense coastal NPF events initiated by iodine nucleation, but particle growth to cloud condensation nuclei (CCN) sizes was dominated by organic compounds. This article reveals a new group of C18,30HhOoNn and C20,24,28,33HhOo compounds with specific double-bond equivalents and oxygen atom numbers in new sub 20 nm coastal iodine particles by using ultrahigh-resolution Fourier transform–ion cyclotron resonance mass spectrometry (FT-ICR-MS). We proposed these compounds are oxygenated or nitrated products of long-chain unsaturated fatty acids, fatty alcohols, nonprotein amino acids or amino alcohols emitted mutually with iodine from coastal biota or biologically active sea surface. Group contribution method estimated that the addition of –ONO2, –OH and –C=O groups to the precursors reduced their volatility by 2–7 orders of magnitude and thus made their products condensable onto new iodine particles in the coastal atmosphere. Nontarget MS analysis also provided a list of 440 formulas of iodinated organic compounds in size-resolved aerosol samples during the iodine NPF days, which facilitates the understanding of unknown aerosol chemistry of iodine.

scholarly journals Boreal forest BVOC exchange: emissions versus in-canopy sinks

2017 ◽  
Vol 17 (23) ◽  
pp. 14309-14332 ◽  
Author(s):  
Putian Zhou ◽  
Laurens Ganzeveld ◽  
Ditte Taipale ◽  
Üllar Rannik ◽  
Pekka Rantala ◽  
...  
Keyword(s):  
Boreal Forest ◽  
Dry Deposition ◽  
Large Scale ◽  
Transport Model ◽  
Oxidation Products ◽  
Forest Site ◽  
Chemical Production ◽  
Chemical Transport Model ◽  
Understorey Vegetation ◽  
Sources And Sinks

Abstract. A multilayer gas dry deposition model has been developed and implemented into a one-dimensional chemical transport model SOSAA (model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition, and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g. monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes, and oxidation products of mono- and sesquiterpenes) in July 2010 at the boreal forest site SMEAR II (Station for Measuring Ecosystem–Atmosphere Relations). According to the significance of modelled monthly-averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: 1. Most of emitted gases are transported out of the canopy (monoterpenes, isoprene + MBO). 2. Chemical reactions remove a significant portion of emitted gases (sesquiterpenes). 3. Bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde). 4. Gases removed by deposition inside the canopy are compensated for by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH). 5. The chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 0.2 hc (canopy height) for oxidation products and above about 0.4 hc for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understorey vegetation) contributed 11–61 % to the overall in-canopy deposition. The emission sources peaked at about 0.8–0.9 hc, which was higher than 0.6 hc where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modelling system, this study analysed both the temporal and spatial variations in individual in-canopy sources and sinks, as well as their combined effects on driving BVOC exchange. In this study 12 featured BVOCs or BVOC groups were analysed. Other compounds could also be investigated similarly by being classified into these five categories.

scholarly journals Contribution from biogenic organic compounds to particle growth during the 2010 BEACHON-ROCS campaign in a Colorado temperate needleleaf forest

2015 ◽  
Vol 15 (15) ◽  
pp. 8643-8656 ◽  
Author(s):  
L. Zhou ◽  
R. Gierens ◽  
A. Sogachev ◽  
D. Mogensen ◽  
J. Ortega ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Ultrafine Particles ◽  
Cloud Condensation Nuclei ◽  
Sulfuric Acid Concentration ◽  
Rocky Mountain ◽  
Particle Growth ◽  
Reaction Rates ◽  
Oxidation Products ◽  
Growth Step ◽  
Sink Term

Abstract. New particle formation (NPF) is an important atmospheric phenomenon. During an NPF event, particles first form by nucleation and then grow further in size. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. Among various physical and chemical processes contributing to particle growth, condensation by organic vapors has been suggested as important. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS (Bio–hydro–atmosphere interactions of Energy, Aerosol, Carbon, H2O, Organics & Nitrogen – Rocky Mountain Organic Carbon Study) campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid western USA. With the latest Criegee intermediate reaction rates implemented in the chemistry scheme, the model underestimates sulfuric acid concentration by 50 %, suggesting either missing sources of atmospheric sulfuric acid or an overestimated sink term. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly, while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in the daytime appears to be closely related to the OH oxidation products of MBO.

scholarly journals Boreal forest BVOCs exchange: emissions versus in-canopy sinks

2017 ◽  
Author(s):  
Putian Zhou ◽  
Laurens Ganzeveld ◽  
Ditte Taipale ◽  
Üllar Rannik ◽  
Pekka Rantala ◽  
...  
Keyword(s):  
Boreal Forest ◽  
Dry Deposition ◽  
Large Scale ◽  
Transport Model ◽  
Oxidation Products ◽  
Forest Site ◽  
Chemical Production ◽  
Chemical Transport Model ◽  
Canopy Exchange ◽  
Sources And Sinks

Abstract. A multi-layer gas dry deposition model has been developed and implemented into a 1-dimensional chemical transport model SOSAA (a model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g., monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes and oxidation products of mono- and sesquiterpenes) in July, 2010 at the boreal forest site SMEAR II (Station to Measure Ecosystem-Atmosphere Relations II). According to the significance of modeled monthly averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: (1) most of emitted gases are transported out of the canopy (monoterpenes, isoprene+MBO), (2) chemical reactions remove a significant portion of emitted gases (sesquiterpenes), (3) bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde), (4) gases removed by deposition inside the canopy are compensated by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH), and finally (5) the chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 4 m for oxidation products and above about 8 m for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understory vegetation) contributed 11–61 % to the overall in-canopy deposition. The emission sources peaked at about 14–16 m which was higher than 10 m where the maximum of dry deposition onto overstorey vegetation was located. This study provided a method to enable the quantification of the exchange between atmosphere and biosphere for numerous BVOCs, which could be applied in large-scale models in future. With this more explicit canopy exchange modeling system this study analysed both the temporal and spatial variations of individual in-caonpy sources and sinks, as well as their combined effects on driving BVOCs exchange. Twelve featured BVOCs or BVOC groups were analyzed in this study, more compounds could also be investigated similarly by being classified into the five categories.

scholarly journals Size and composition measurements of background aerosol and new particle growth in a Finnish forest during QUEST 2 using an Aerodyne Aerosol Mass Spectrometer

2005 ◽  
Vol 5 (5) ◽  
pp. 8755-8789 ◽  
Author(s):  
J. D. Allan ◽  
M. R. Alfarra ◽  
K. N. Bower ◽  
H. Coe ◽  
J. T. Jayne ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Cloud Condensation Nuclei ◽  
Particle Diameter ◽  
Particle Growth ◽  
Small Mass ◽  
Oxidation Products ◽  
Particle Nucleation ◽  
Aerosol Mass Spectrometer ◽  
Mass Spectral ◽  
Aerosol Mass

Abstract. The study of the growth of nucleation-mode particles is important, as this prevents their loss through diffusion and allows them to reach sizes where they may become effective cloud condensation nuclei. Hyytiälä, a forested site in southern Finland, frequently experiences particle nucleation events during the spring and autumn, where particles first appear during the morning and continue to grow for several hours afterwards. As part of the QUEST 2 intensive field campaign during March and April 2003, an Aerodyne Aerosol Mass Spectrometer (AMS) was deployed alongside other aerosol instrumentation to study the particulate composition and dynamics of growth events and characterise the background aerosol. Despite the small mass concentrations, the AMS was able to distinguish the grown particles in the <100 nm regime several hours after an event and confirm that the particles were principally organic in composition. The AMS was also able to derive a mass spectral fingerprint for the organic species present, and found that it was consistent between events and independent of the mean particle diameter during non-polluted cases, implying the same species were also condensing onto the accumulation mode. The results were compared with those from offline analyses such as GC-MS and were consistent with the hypothesis that the main components were alkanes from plant waxes and the oxidation products of terpenes.

scholarly journals Evolution of particle composition in CLOUD nucleation experiments

2012 ◽  
Vol 12 (12) ◽  
pp. 31071-31105 ◽  
Author(s):  
H. Keskinen ◽  
A. Virtanen ◽  
J. Joutsensaari ◽  
G. Tsagkogeorgas ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Mass Spectrometer ◽  
Volume Fraction ◽  
Cloud Condensation Nuclei ◽  
Time Of Flight ◽  
Particle Diameter ◽  
Particle Growth ◽  
Oxidation Products ◽  
Ion Composition ◽  
Differential Mobility

Abstract. Sulphuric acid, ammonia, amines, and oxidised organics play a crucial role in nanoparticle formation in the atmosphere. In this study, we investigate the composition of nucleated nanoparticles formed from these compounds in the CLOUD chamber experiments at CERN. The investigation is carried out via analysis of the particle hygroscopicity, ethanol affinity, oxidation state, and ion composition. Hygroscopicity was studied by a hygroscopic tandem differential mobility analyser and a cloud condensation nuclei counter, ethanol affinity by an organic differential mobility analyser and particle oxidation level by a high-resolution time-of-flight aerosol mass spectrometer. The ion composition was studied by an atmospheric pressure interface time-of-flight mass spectrometer. The volume fraction of the organics in the particles during their growth from sizes of a few nanometers to tens of nanometers was derived from measured hygroscopicity assuming the Zdanovski-Stokes-Robinson relationship, and compared to values gained from the spectrometers. The ZSR-relationship was also applied to obtain the measured ethanol affinities during the particle growth, which were used to derive the volume fractions of sulphuric acid and the other inorganics (e.g. ammonium salts). In the presence of sulphuric acid and ammonia, particles with a mobility diameter of 150 nm were chemically neutralised to ammonium sulphate. In the presence of oxidation products of pinanediol, the organic volume fraction of freshly nucleated particles increased from 0.4 to ∼0.9, with an increase in diameter from 2 to 63 nm. Conversely, the sulphuric acid volume fraction decreased from 0.6 to 0.1 when the particle diameter increased from 2 to 50 nm. The results provide information on the composition of nucleated aerosol particles during their growth in the presence of various combinations of sulphuric acid, ammonia, dimethylamine and organic oxidation products.

scholarly journals Evolution of particle composition in CLOUD nucleation experiments

2013 ◽  
Vol 13 (11) ◽  
pp. 5587-5600 ◽  
Author(s):  
H. Keskinen ◽  
A. Virtanen ◽  
J. Joutsensaari ◽  
G. Tsagkogeorgas ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Mass Spectrometer ◽  
Volume Fraction ◽  
Cloud Condensation Nuclei ◽  
Time Of Flight ◽  
Particle Diameter ◽  
Particle Growth ◽  
Oxidation Products ◽  
Ion Composition ◽  
Differential Mobility

Abstract. Sulphuric acid, ammonia, amines, and oxidised organics play a crucial role in nanoparticle formation in the atmosphere. In this study, we investigate the composition of nucleated nanoparticles formed from these compounds in the CLOUD (Cosmics Leaving Outdoor Droplets) chamber experiments at CERN (Centre européen pour la recherche nucléaire). The investigation was carried out via analysis of the particle hygroscopicity, ethanol affinity, oxidation state, and ion composition. Hygroscopicity was studied by a hygroscopic tandem differential mobility analyser and a cloud condensation nuclei counter, ethanol affinity by an organic differential mobility analyser and particle oxidation level by a high-resolution time-of-flight aerosol mass spectrometer. The ion composition was studied by an atmospheric pressure interface time-of-flight mass spectrometer. The volume fraction of the organics in the particles during their growth from sizes of a few nanometers to tens of nanometers was derived from measured hygroscopicity assuming the Zdanovskii–Stokes–Robinson relationship, and compared to values gained from the spectrometers. The ZSR-relationship was also applied to obtain the measured ethanol affinities during the particle growth, which were used to derive the volume fractions of sulphuric acid and the other inorganics (e.g. ammonium salts). In the presence of sulphuric acid and ammonia, particles with a mobility diameter of 150 nm were chemically neutralised to ammonium sulphate. In the presence of oxidation products of pinanediol, the organic volume fraction of freshly nucleated particles increased from 0.4 to ~0.9, with an increase in diameter from 2 to 63 nm. Conversely, the sulphuric acid volume fraction decreased from 0.6 to 0.1 when the particle diameter increased from 2 to 50 nm. The results provide information on the composition of nucleated aerosol particles during their growth in the presence of various combinations of sulphuric acid, ammonia, dimethylamine and organic oxidation products.

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