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Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
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Volume 15, issue 5 | Copyright
Atmos. Chem. Phys., 15, 2775-2790, 2015
https://doi.org/10.5194/acp-15-2775-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 10 Mar 2015

Research article | 10 Mar 2015

A critical evaluation of proxy methods used to estimate the acidity of atmospheric particles

C. J. Hennigan1, J. Izumi1, A. P. Sullivan2, R. J. Weber3, and A. Nenes3,4,5 C. J. Hennigan et al.
  • 1Department of Chemical, Biochemical and Environmental Engineering, University of Maryland, Baltimore County, Baltimore, MD, USA
  • 2Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA
  • 3School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA
  • 4School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA
  • 5Foundation for Research and Technology – Hellas, Patras, Greece

Abstract. Given significant challenges with available measurements of aerosol acidity, proxy methods are frequently used to estimate the acidity of atmospheric particles. In this study, four of the most common aerosol acidity proxies are evaluated and compared: (1) the ion balance method, (2) the molar ratio method, (3) thermodynamic equilibrium models, and (4) the phase partitioning of ammonia. All methods are evaluated against predictions of thermodynamic models and against direct observations of aerosol–gas equilibrium partitioning acquired in Mexico City during the Megacity Initiative: Local and Global Research Objectives (MILAGRO) study. The ion balance and molar ratio methods assume that any deficit in inorganic cations relative to anions is due to the presence of H+ and that a higher H+ loading and lower cation / anion ratio both correspond to increasingly acidic particles (i.e., lower pH). Based on the MILAGRO measurements, no correlation is observed between H+ levels inferred with the ion balance and aerosol pH predicted by the thermodynamic models and NH3–NH4+ partitioning. Similarly, no relationship is observed between the cation / anion molar ratio and predicted aerosol pH. Using only measured aerosol chemical composition as inputs without any constraint for the gas phase, the E-AIM (Extended Aerosol Inorganics Model) and ISORROPIA-II thermodynamic equilibrium models tend to predict aerosol pH levels that are inconsistent with the observed NH3–NH4+ partitioning. The modeled pH values from both E-AIM and ISORROPIA-II run with gas + aerosol inputs agreed well with the aerosol pH predicted by the phase partitioning of ammonia. It appears that (1) thermodynamic models constrained by gas + aerosol measurements and (2) the phase partitioning of ammonia provide the best available predictions of aerosol pH. Furthermore, neither the ion balance nor the molar ratio can be used as surrogates for aerosol pH, and previously published studies with conclusions based on such acidity proxies may need to be reevaluated. Given the significance of acidity for chemical processes in the atmosphere, the implications of this study are important and far reaching.

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We show that the ion balance and molar ratio methods are unsuitable for use as aerosol pH proxies. Our recommendation is that 1) thermodynamic equilibrium models constrained by both gas and aerosol inputs run in the forward (open) mode, and 2) the phase partitioning of ammonia provides the best predictions of aerosol pH. Given the significance of acidity for numerous chemical processes in the atmosphere, the implications of this study are important and far reaching.
We show that the ion balance and molar ratio methods are unsuitable for use as aerosol pH...
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