Heteromolecular nucleation in the sulfuric acid-water system

Jaecker-Voirol, A.; Mirabel, Philippe

doi:10.1016/0004-6981(89)90530-1

Cited by 183 publications

(84 citation statements)

References 22 publications

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“…Five nucleation or direct NPF parameterizations can be chosen in MATRIX, two for binary homogeneous nucleation of H 2 SO 4 -H 2 O (Jaecker- Voirol and Mirabel, 1989;Vehkamäki et al, 2002), one for ternary homogeneous nucleation of H 2 SO 4 -NH 3 -H 2 O , one for nucleation by ion-ion recombination (Turco et al, 1998), and one for formation of particles of 3-nm diameter derived from field observations (Eisele and McMurry, 1997). The ionion recombination mechanism is taken as independent of the homogeneous mechanisms, and the ion-ion recombination Atmos.…”

Section: New Particle Formationmentioning

confidence: 99%

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MATRIX (Multiconfiguration Aerosol TRacker of mIXing state): an aerosol microphysical module for global atmospheric models

et al. 2008

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Abstract.A new aerosol microphysical module MATRIX, the Multiconfiguration Aerosol TRacker of mIXing state, and its application in the Goddard Institute for Space Studies (GISS) climate model (ModelE) are described. This module, which is based on the quadrature method of moments (QMOM), represents nucleation, condensation, coagulation, internal and external mixing, and cloud-drop activation and provides aerosol particle mass and number concentration and particle size information for up to 16 mixed-mode aerosol populations. Internal and external mixing among aerosol components sulfate, nitrate, ammonium, carbonaceous aerosols, dust and sea-salt particles are represented. The solubility of each aerosol population, which is explicitly calculated based on its soluble and insoluble components, enables calculation of the dependence of cloud drop activation on the microphysical characterization of multiple soluble aerosol populations.A detailed model description and results of box-model simulations of various aerosol population configurations are presented. The box model experiments demonstrate the dependence of cloud activating aerosol number concentration on the aerosol population configuration; comparisons to sectional models are quite favorable. MATRIX is incorporated into the GISS climate model and simulations are carried out primarily to assess its performance/efficiency for global-scale atmospheric model application. Simulation results were compared with aircraft and station measurements of aerosol mass and number concentration and particle size to assess the ability of the new method to yield data suitable for such comparison. The model accurately captures the observed size distributions in the Aitken and accumulation Correspondence to: S. E. Bauer (sbauer@giss.nasa.gov) modes up to particle diameter 1 µm, in which sulfate, nitrate, black and organic carbon are predominantly located; however the model underestimates coarse-mode number concentration and size, especially in the marine environment. This is more likely due to oversimplifications of the representation of sea salt emissions -sea salt emissions are only calculated for two size classes -than to inherent limitations of MA-TRIX.

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Section: New Particle Formationmentioning

confidence: 99%

“…-The Jaecker- Voirol and Mirabel (1989) (Usoskin and Kovaltsov, 2006) are not considered in the current model. The ionization rate is an upper limit on the nucleation rate.…”

Section: New Particle Formationmentioning

confidence: 99%

MATRIX (Multiconfiguration Aerosol TRacker of mIXing state): an aerosol microphysical module for global atmospheric models

et al. 2008

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“…These mechanisms include: binary nucleation in which sulfuric acid vapor and water vapor condense to form the new particles (Jacker-Voirol and Mirabel, 1989;Kulmala et al, 1998;Vehkamäki et al, 2002), ternary nucleation in which sulfuric acid vapor, ammonia and water vapor condense to form the new particles Anttila et al, 2005;Yu, 2006b) and ion-induced nucleation in which gas-phase ions aid in either binary or ternary nucleation (Yu and Turco, 2001;Laakso et al, 2002;Kazil and Lovejoy, 2004;Lovejoy et al, 2004;Kazil et al, 2006;Yu, 2006a). Additionally, cluster activation theory has been proposed to explain the dependence of nucleation rate on sulfuric acid concentrations in the boundary layer Sihto et al, 2006).…”

Section: Introductionmentioning

confidence: 99%

Uncertainty in global CCN concentrations from uncertain aerosol nucleation and primary emission rates

2009

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Abstract. The indirect effect of aerosols on climate is highly uncertain and limits our ability to assess anthropogenic climate change. The foundation of this uncertainty is uncertainty in the number of cloud condensation nuclei (CCN), which itself stems from uncertainty in aerosol nucleation, primary emission and growth rates. In this paper, we use a global general circulation model with aerosol microphysics to assess how the uncertainties in aerosol nucleation, emission and growth rates affect our prediction of CCN(0.2%) concentrations. Using several nucleation rate parameterizations that span six orders of magnitude of globally averaged nucleation rates, the tropospheric average CCN(0.2%) concentrations vary by 17% and the boundary layer average vary by 12%. This sensitivity of tropospheric average CCN(0.2%) to the nucleation parameterizations increases to 33% and 20% when the total primary emissions are reduced by a factor of 3 and the SOA condensation rates are increased by a factor of 3.5, respectively. These results show that it is necessary to better understand global nucleation rates when determining CCN concentrations. When primary emissions rates are varied by a factor of 3 while using a binary nucleation parameterization, tropospheric average CCN(0.2%) concentrations also vary by 17%, but boundary layer average vary by 40%. Using the fastest nucleation rate parameterization, these changes drop to 3% and 22%, respectively. These results show the importance of reducing uncertainties in primary emissions, which appear from these results to be somewhat more important for CCN than the much larger uncertainties in nucleation. These results also show that uncertainties in nucleation and primary emissions are more important when sufficient condensable material is available to Correspondence to: J. R. Pierce (jeffrey.robert.pierce@gmail.com) grow them to CCN sizes. The percent change in CCN(0.2%) concentration between pre-industrial times and present day does not depend greatly on the nucleation rate parameterization used for our base case scenarios; however, because other factors, such as primary emissions and SOA, are uncertain in both time periods, this may be a coincidence.

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“…One of the most important binary nucleating systems is H 2 SO 4 /H 2 O, to which numerous papers are devoted on both theoretical [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] and experimental [27][28][29][30][31][32] fronts. Comparisons of the classical predictions with experimental data for H 2 SO 4 /H 2 O nucleation, while not extensive, yield conflicting results as to the validity of the classical theory.…”

Section: Introductionmentioning

confidence: 99%

Binary nucleation of sulfuric acid-water: Monte Carlo simulation

Kusaka

Wang

Seinfeld

1998

The Journal of Chemical Physics

104

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We have developed a classical mechanical model for the H 2 SO 4 /H 2 O binary system. Monte Carlo simulation was performed in a mixed ensemble, in which the number of sulfuric acid molecules is fixed while that of water molecules is allowed to fluctuate. Simulation in this ensemble is computationally efficient compared to conventional canonical simulation, both in sampling very different configurations of clusters relevant in nucleation and in evaluating the free energy of cluster formation. The simulation yields molecular level information, such as the shape of the clusters and the dissociation behavior of the acid molecule in the cluster. Our results indicate that the clusters are highly nonspherical as a result of the anisotropic intermolecular interactions and that a cluster with a given number of acid molecules has several very different conformations, which are close in free energy and hence equally relevant in nucleation. The dissociation behavior of H 2 SO 4 in a cluster differs markedly from that in bulk solution and depends sensitively on the assumed value of the free energy f hb of the dissociation reaction H 2 SO 4 ϩH 2 O→HSO 4In a small cluster, no dissociation is observed. As the cluster size becomes larger, the probability of having an HSO 4ϩ ion pair increases. However, in clusters relevant in nucleation, the resulting ion pairs remain in contact; about 240 water molecules are required to observe behavior that resembles that in bulk solution. If a larger value of f hb is assumed to reflect its uncertainty, the probability of dissociation becomes negligible. A reversible work surface obtained for a condition typical of vapor to liquid nucleation suggests that the rate-limiting step of new particle formation is a binary collision of two hydrated sulfuric acid molecules. The ion pairs formed by dissociation play a key role in stabilizing the resulting cluster. The reversible work surface is sensitive to the assumed value of f hb , thus pointing to the need for an accurate estimate of the quantity either by ab initio calculations or experiments.

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Heteromolecular nucleation in the sulfuric acid-water system

Cited by 183 publications

References 22 publications

MATRIX (Multiconfiguration Aerosol TRacker of mIXing state): an aerosol microphysical module for global atmospheric models

MATRIX (Multiconfiguration Aerosol TRacker of mIXing state): an aerosol microphysical module for global atmospheric models

Uncertainty in global CCN concentrations from uncertain aerosol nucleation and primary emission rates

Binary nucleation of sulfuric acid-water: Monte Carlo simulation

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