scholarly journals New particle formation from sulfuric acid and ammonia: nucleation and growth model based on thermodynamics derived from CLOUD measurements for a wide range of conditions

2019 ◽  
Vol 19 (7) ◽  
pp. 5033-5050 ◽  
Author(s):  
Andreas Kürten
Keyword(s):  
Sulfuric Acid ◽  
Growth Model ◽  
Thermodynamic Data ◽  
Particle Formation ◽  
Nucleation And Growth ◽  
Aerosol Size Distribution ◽  
Formation Mechanisms ◽  
Strong Impact ◽  
New Particle Formation ◽  
Wide Range

Abstract. Understanding new particle formation and growth is important because of the strong impact of these processes on climate and air quality. Measurements to elucidate the main new particle formation mechanisms are essential; however, these mechanisms have to be implemented in models to estimate their impact on the regional and global scale. Parameterizations are computationally cheap ways of implementing nucleation schemes in models, but they have their limitations, as they do not necessarily include all relevant parameters. Process models using sophisticated nucleation schemes can be useful for the generation of look-up tables in large-scale models or for the analysis of individual new particle formation events. In addition, some other important properties can be derived from a process model that implicitly calculates the evolution of the full aerosol size distribution, e.g., the particle growth rates. Within this study, a model (SANTIAGO – Sulfuric acid Ammonia NucleaTIon And GrOwth model) is constructed that simulates new particle formation starting from the monomer of sulfuric acid up to a particle size of several hundred nanometers. The smallest sulfuric acid clusters containing one to four acid molecules and a varying amount of base (ammonia) are allowed to evaporate in the model, whereas growth beyond the pentamer (five sulfuric acid molecules) is assumed to be entirely collision-controlled. The main goal of the present study is to derive appropriate thermodynamic data needed to calculate the cluster evaporation rates as a function of temperature. These data are derived numerically from CLOUD (Cosmics Leaving OUtdoor Droplets) chamber new particle formation rates for neutral sulfuric acid–water–ammonia nucleation at temperatures between 208 and 292 K. The numeric methods include an optimization scheme to derive the best estimates for the thermodynamic data (dH and dS) and a Monte Carlo method to derive their probability density functions. The derived data are compared to literature values. Using different data sets for dH and dS in SANTIAGO detailed comparison between model results and measured CLOUD new particle formation rates is discussed.

scholarly journals New particle formation from sulfuric acid and ammonia: nucleation and growth model based on thermodynamics derived from CLOUD measurements for a wide range of conditions

2019 ◽  
Author(s):  
Andreas Kürten
Keyword(s):  
Sulfuric Acid ◽  
Growth Model ◽  
Thermodynamic Data ◽  
Particle Formation ◽  
Nucleation And Growth ◽  
Aerosol Size Distribution ◽  
Formation Mechanisms ◽  
Strong Impact ◽  
New Particle Formation ◽  
Wide Range

Abstract. Understanding new particle formation and growth is important because of the strong impact of these processes on climate and air quality. Measurements to elucidate the main new particle formation mechanisms are essential; however, these mechanisms have to be implemented in models to estimate their impact on the regional and global scale. Parameterizations are computationally cheap ways of implementing nucleation schemes in models but they have their limitations, as they do not necessarily include all relevant parameters. Process models using sophisticated nucleation schemes can be useful for the generation of look-up tables in large-scale models or for the analysis of individual new particle formation events. In addition, some other important properties can be derived from a process model that implicitly calculates the evolution of the full aerosol size distribution, e.g., the particle growth rates. Within this study, a model (SANTIAGO, Sulfuric acid Ammonia NucleaTIon And GrOwth model) is constructed that simulates new particle formation starting from the monomer of sulfuric acid up to a particle size of several hundred nanometers. The smallest sulfuric acid clusters containing one to four acid molecules and varying amount of base (ammonia) are allowed to evaporate in the model, whereas growth beyond the pentamer (5 sulfuric acid molecules) is assumed to be entirely collision-controlled. The main goal of the present study is to derive appropriate thermodynamic data needed to calculate the cluster evaporation rates as a function of temperature. These data are derived numerically from CLOUD (Cosmics Leaving OUtdoor Droplets) chamber new particle formation rates for neutral sulfuric acid-water-ammonia nucleation at temperatures between 208 K and 292 K. The numeric methods include an optimization scheme to derive the best estimates for the thermodynamic data (dH and dS) and a Monte Carlo method to derive their probability density functions. The derived data are compared to literature values. Using different data sets for dH and dS in SANTIAGO detailed comparison between model results and measured CLOUD new particle formation rates is discussed.

Improved identification of evaporation rates and thermodynamic data by Monte-Carlo method

2020 ◽  
Author(s):  
Anna Shcherbacheva ◽  
Tapio Helin ◽  
Heikki Haario ◽  
Hanna Vehkamäki
Keyword(s):  
Monte Carlo ◽  
Sulfuric Acid ◽  
Thermodynamic Data ◽  
Particle Formation ◽  
Forward Problem ◽  
Dependent Data ◽  
New Particle Formation ◽  
Free Energies ◽  
Wide Range ◽  
Cluster Composition

<p>Atmospheric new particle formation and successive cluster growth to aerosol particles is an important field of research, in particular due to climate change phenomena and air quality monitoring. Recent developments in the instrumentation have enabled quantification of ionic clusters formed in the gas phase at the first steps of particle formation under atmospherically relevant mixing ratios. However, electrically neutral clusters are prevalent in atmospheric conditions, and thus must be charged prior to detection by mass spectrometer. The charging process can lead to cluster fragmentation and thus alter the measured cluster composition.</p><p>Even when the cluster composition can be measured directly, this does not quantify individual cluster-level properties, such as cluster collision and evaporation rates. Collision rates contain relatively small uncertainties in comparison to evaporation rates, which are computed using detailed balance assumption together with the free energies of cluster formation, which can in turn be obtained from Quantum chemistry (QC) methods. As evaporation rates depend exponentially on the free energies, even difference by several kcal/mol between different QC methods results in orders of magnitude differences in evaporation rates.</p><p>On the other hand, in spite of the error margins associated with the evaporation rates, simulations of cluster populations, which incorporate collision and evaporation rates as free parameters (such as Becker-Döring models), have demonstrated good qualitative agreement with experimental data. The Becker-Döring equations are a system of Ordinary Differential equations (ODE) which account for cluster birth and death processes, as well as external sinks and sources. In mathematical terms, prediction of cluster concentrations using kinetic simulations with given cluster collision and evaporation rates is called a forward problem.</p><p>In the present study, we focus on the so-called inverse problem of how to derive the evaporation rates and thermodynamic data (enthalpy change and entropy change due to addition or removal of molecule) from available measurements, rather than on the forward problem. We do this by Delayed Rejection Adaptive Monte Carlo (DRAM) method for the system containing sulfuric acid and ammonia with the maximal size of the pentamer. Initially, we tested the method on the synthetic data created from Atmospheric Cluster Dynamic Code (ACDC) simulations. By so doing, we identify the combination of fitted parameters and concentration measurements, which leads to the best identification of the evaporation rates. Additionally, we demonstrated that the temperature-dependent data yield better estimates of the evaporation rates as compared to the time-dependent data measured before the system has reached the steady state.</p><p>Next, we apply the technique to improve the identification of the evaporation rates from CLOUD chamber data, which contain cluster concentrations and new particle formation rates measured at different temperatures and a wide range of atmospherically relevant sulfuric acid and ammonia concentrations. As a result, we were able to obtain the probability density functions (PDFs) that show small standard variations for thermodynamic data. By using the values from the PDFs as parameters in the ACDC model, we achieve a fair agreement with the measured NPFs and cluster concentrations for a wide range of temperatures.</p>

scholarly journals New particle formation in the sulfuric acid–dimethylamine–water system: reevaluation of CLOUD chamber measurements and comparison to an aerosol nucleation and growth model

2018 ◽  
Vol 18 (2) ◽  
pp. 845-863 ◽  
Author(s):  
Andreas Kürten ◽  
Chenxi Li ◽  
Federico Bianchi ◽  
Joachim Curtius ◽  
António Dias ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Detection Threshold ◽  
Sulfuric Acid Concentration ◽  
Water System ◽  
Particle Formation ◽  
New Particle Formation ◽  
Flow Tube ◽  
Aerosol Model ◽  
Wide Range ◽  
Good Agreement

Abstract. A recent CLOUD (Cosmics Leaving OUtdoor Droplets) chamber study showed that sulfuric acid and dimethylamine produce new aerosols very efficiently and yield particle formation rates that are compatible with boundary layer observations. These previously published new particle formation (NPF) rates are reanalyzed in the present study with an advanced method. The results show that the NPF rates at 1.7 nm are more than a factor of 10 faster than previously published due to earlier approximations in correcting particle measurements made at a larger detection threshold. The revised NPF rates agree almost perfectly with calculated rates from a kinetic aerosol model at different sizes (1.7 and 4.3 nm mobility diameter). In addition, modeled and measured size distributions show good agreement over a wide range of sizes (up to ca. 30 nm). Furthermore, the aerosol model is modified such that evaporation rates for some clusters can be taken into account; these evaporation rates were previously published from a flow tube study. Using this model, the findings from the present study and the flow tube experiment can be brought into good agreement for the high base-to-acid ratios (∼ 100) relevant for this study. This confirms that nucleation proceeds at rates that are compatible with collision-controlled (a.k.a. kinetically controlled) NPF for the conditions during the CLOUD7 experiment (278 K, 38 % relative humidity, sulfuric acid concentration between 1 × 106 and 3 × 107 cm−3, and dimethylamine mixing ratio of ∼ 40 pptv, i.e., 1 × 109 cm−3).

scholarly journals Observation of aerosol size distribution and new particle formation at a mountain site in subtropical Hong Kong

2012 ◽  
Vol 12 (20) ◽  
pp. 9923-9939 ◽  
Author(s):  
H. Guo ◽  
D. W. Wang ◽  
K. Cheung ◽  
Z. H. Ling ◽  
C. K. Chan ◽  
...  
Keyword(s):  
Growth Rate ◽  
Hong Kong ◽  
Sulfuric Acid ◽  
Size Distribution ◽  
Formation Rate ◽  
Particle Formation ◽  
Aerosol Size Distribution ◽  
New Particle Formation ◽  
Average Growth ◽  
Nucleation Mode

Abstract. In order to investigate the formation and growth processes of nucleation mode particles, and to quantify the particle number (PN) concentration and size distributions in Hong Kong, an intensive field measurement was conducted from 25 October to 29 November in 2010 near the mountain summit of Tai Mo Shan, a suburban site approximately the geographical centre of the New Territories in Hong Kong. Based on observations of the particle size distribution, new particle formation (NPF) events were found on 12 out of 35 days with the estimated formation rate J5.5 from 0.97 to 10.2 cm−3 s−1, and the average growth rates from 1.5 to 8.4 nm h−1. The events usually began at 10:00–11:00 LT characterized by the occurrence of a nucleation mode with a peak diameter of 6–10 nm. Solar radiation, wind speed, sulfur dioxide (SO2) and ozone (O3) concentrations were on average higher, whereas temperature, relative humidity and daytime nitrogen dioxide (NO2) concentration were lower on NPF days than on non-NPF days. Back trajectory analysis suggested that in majority of the NPF event days, the air masses originated from the northwest to northeast directions. The concentrations of gaseous sulfuric acid (SA) showed good power-law relationship with formation rates, with exponents ranging from 1 to 2. The result suggests that the cluster activation theory and kinetic nucleation could potentially explain the observed NPF events in this mountainous atmosphere of Hong Kong. Meanwhile, in these NPF events, the contribution of sulfuric acid vapor to particle growth rate (GR5.5–25) ranged from 9.2 to 52.5% with an average of 26%. Measurement-based calculated oxidation rates of monoterpenes (i.e. α-pinene, β-pinene, myrcene and limonene) by O3 positively correlated with the GR5.5–25 (R = 0.80, p < 0.05). The observed associations of the estimated formation rate J5.5 and the growth rate GR5.5–25 with gaseous sulfuric acid and volatile organic compounds (VOCs) suggested the critical roles of sulfuric acid and biogenic VOCs (e.g. α-pinene and β-pinene) in these NPF events.

scholarly journals On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

2014 ◽  
Vol 14 (9) ◽  
pp. 13413-13464 ◽  
Author(s):  
S. Schobesberger ◽  
A. Franchin ◽  
F. Bianchi ◽  
L. Rondo ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Sulfuric Acid ◽  
Gas Phase ◽  
Particle Formation ◽  
Atmospheric Conditions ◽  
New Particle Formation ◽  
Acid Base ◽  
Wide Range ◽  
Charged Clusters ◽  
Positively Charged

Abstract. 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.

scholarly journals New particle formation in the sulfuric acid-dimethy lamine-water system: Reevaluation of CLOUD chamber measurements and comparison to an aerosol nucleation and growth model

2017 ◽  
Author(s):  
Andreas Kürten ◽  
Chenxi Li ◽  
Federico Bianchi ◽  
Joachim Curtius ◽  
António Dias ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Sulfuric Acid ◽  
Detection Threshold ◽  
Sulfuric Acid Concentration ◽  
Particle Formation ◽  
New Particle Formation ◽  
Flow Tube ◽  
Aerosol Model ◽  
Wide Range ◽  
Good Agreement

Abstract. A recent CLOUD (Cosmics Leaving OUtdoor Droplets) chamber study showed that sulfuric acid and dimethylamine produce new aerosols very efficiently, and yield particle formation rates that are compatible with boundary layer observations. These previously published new particle formation (NPF) rates are re-analyzed in the present study with an advanced method. The results show that the NPF rates at 1.7 nm are more than a factor of 10 faster than previously published due to earlier approximations in correcting particle measurements made at larger detection threshold. The revised NPF rates agree almost perfectly with calculated rates from a kinetic aerosol model at different sizes (1.7 nm and 4.3 nm mobility diameter). In addition, modeled and measured size distributions show good agreement over a wide range (up to ca. 30 nm). Furthermore, the aerosol model is modified such that evaporation rates for some clusters can be taken into account; these evaporation rates were previously published from a flow tube study. Using this model, the findings from the present study and the flow tube experiment can be brought into good agreement. This confirms that nucleation proceeds at rates that are compatible with collision-controlled (a.k.a. kinetically-controlled) new particle formation for the conditions during the CLOUD7 experiment (278 K, 38 % RH, sulfuric acid concentration between 1 × 106 and 3 × 107 cm−3 and dimethylamine mixing ratio of ~ 40 pptv). Finally, the simulation of atmospheric new particle formation reveals that even tiny mixing ratios of dimethylamine (0.1 pptv) yield NPF rates that could explain significant boundary layer particle formation. This highlights the need for improved speciation and quantification techniques for atmospheric gas-phase amine measurements.

scholarly journals On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

2015 ◽  
Vol 15 (1) ◽  
pp. 55-78 ◽  
Author(s):  
S. Schobesberger ◽  
A. Franchin ◽  
F. Bianchi ◽  
L. Rondo ◽  
J. Duplissy ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Sulfuric Acid ◽  
Gas Phase ◽  
Particle Formation ◽  
Atmospheric Conditions ◽  
New Particle Formation ◽  
Acid Base ◽  
Wide Range ◽  
Charged Clusters ◽  
Positively Charged

Abstract. 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.

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