References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-9-9551-2009

A comparison of water uptake by aerosols using two thermodynamic models

¹ Penner

J. E.

¹ Metzger

² Lelieveld

Department of Atmospheric, Oceanic and Space Science, University of Michigan, Ann Arbor, Michigan, USA

Max Planck Institute for Chemistry, Mainz, Germany

16 04 2009

9 2 9551 9595

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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A comprehensive comparison between two aerosol thermodynamic equilibrium models used in chemistry-climate simulations, EQUISOLV II and EQSAM3, is conducted for various relative humidities and chemical compositions. Our results show that the concentration of total particulate matter as well as the associated aerosol liquid water content predicted by these two models is comparable for all conditions, which is important for radiative forcing estimates. The normalized absolute difference in the concentration of total particulate matter is 6% on average for all 200 conditions studied, leading to a regression coefficient of about 0.8 for the water associated with the aerosol between these two models. Relatively large discrepancies occur, however, at high ammonium, low nitrate/sodium concentrations at low and medium relative humidities (RH<60–70%), which is analyzed and discussed in detail. In addition, the prediction of the partitioning of ammonium and nitrate is investigated under realistic atmospheric conditions. The data collected during the Mediterranean Intensive Oxidant Study (MINOS) campaign are simulated using both models. The results show that both models can reproduce the concentration of total particulate matter for 90% of the time within a factor of 2, while the predicted concentration of aerosol water by these two models is significantly correlated. The largest difference exists near RH's of 70–80% which is the RH range for the transition of mixed ammonium salts from the solid to the liquid phase.

References 1

Adams,~P J., Seinfeld,~J H., and Koch,~D M.: Global concentration of tropospheric sulfate, nitrate, and ammonium aerosol simulated in a~general circulate model, J. Geophys. Res., 104, 13791–13823, 1999.

Ansari,~A S. and Pandis,~S N.: Prediction of multicomponent inorganic atmospheric aerosol behavior, Atmos. Environ., 33, 745–757, 1999a.

Ansari,~A S. and Pandis,~S N.: An analysis of four models predicting the partitioning of semivolatile inorganic aerosol components, Aeros. Sci. Tech., 31, 129–153, 1999b.

Ansari,~A S. and Pandis,~S N.: The effect of metastable equilibrium states on the partitioning of nitrate between the gas and aerosol phases, Atmos. Environ., 34, 157–168, 2000.

Amundson, N. R., Caboussat, A., He, J. W., Martynenko, A. V., Savarin, V. B., Seinfeld, J. H., and Yoo, K. Y.: A new inorganic atmospheric aerosol phase equilibrium model (UHAERO), Atmos. Chem. Phys., 6, 975–992, 2006.

Bassett,~M E. and Seinfeld,~J H.: Atmospheric equilibrium models of sulfate and nitrate aerosol II, Particle size analysis, Atmos., Environ., 18, 1163–1170, 1983.

Bassett,~M E. and Seinfeld,~J H.: Atmospheric equilibrium models of sulfate and nitrate aerosol, Atmos. Environ., 17, 2238–2252, 1984.

Bromley,~L A.: Thermodynamic properties of strong electrolytes in aqueous solutions, AI. Ch E. Journal 19, 313–320, 1973.

Clegg,~S L., Pitzer,~K S., and Brimblecombe,~P.: Thermodynamics of multicomponent, miscible, ionic solutions. II. Mixture including unsymmetrical electrolytes, J. Phys. Chem,, 96, 9470–9479, 1992.

Clegg,~S L., Pitzer,~K S., and Brimblecombe,~P.: Additions and corrections for their published papers, J. Phys. Chem., 98, P 1368, 1994.

Clegg,~S L., Pitzer,~K S. and Brimblecombe,~P.: Additions and corrections for their published papers, J. Phys. Chem., 99, p 6755, 1995.

Clegg,~S L., Brimblecombe,~P., and Wexler,~A S.: A~thermodynamic model of the system \chemH^+-\chemNH_4^+-\chemNa^+-\chemSO_4^2-\chemNO_3^-\chemCl^-\chemH_2O at 298.15 \unitK, J. Phys. Chem., 102, 2155–2171, 1998a.

Clegg,~S L., Brimblecombe,~P., and Wexler,~A S.: A~thermodynamic model of the system \chemH^+-\chemNH_4^+-\chemNa^+-\chemSO_4^2-\chemNO_3^-\chemCl^-\chemH_2O at tropospheric temperatures, J. Phys. Chem., 102, 2137–2154, 1998b.

Feng, Y. and Penner,~J E.: Global modeling of nitrate and ammonium: Interaction of aerosols and tropospheric chemistry,~J. Geophys. Res., 112, D01304, doi:10.1029/2005JD006404, 2007.

Fountoukis, C. and Nenes, A.: ISORROPIA II: a computationally efficient thermodynamic equilibrium model for \chemK^+-\chemCa^2+-\chemMg^2+-\chemNH_4^+-\chemNa^+-\chemSO_4^2-\chemNO_3^-\chemCl^-\chemH_2O aerosols, Atmos. Chem. Phys., 7, 4639–4659, 2007.

Harned,~H S. and Owen,~B B.: The Physical Chemistry of Electrolyte solutions, Reinhold, New York, Chap 8, 1958.

Jacobson,~M Z., Tabazadeh,~A., and Turco,~R.: Simulating equilibrium within aerosols and nonequilibrium between gases and aerosols, J. Geophys. Res., 101(D4), 9079–9091. 1996.

Jacobson,~M Z.: Studying the effects of calcium and magnesium on size-distributed nitrate and ammonium with EQUISOLV II, Atmos. Environ., 33, 3635–3649, 1999.

Jacobson,~M Z.: Fundamentals of Atmospheric Modeling, Cambridge University Press, 2005.

Kim,~Y P., Seinfeld,~J H., and Saxena,~P.: Atmospheric gas aerosol equilibrium, I: thermodynamic model, Aerosol Sci. Technol. 19, 157–181, 1993a.

Kim,~Y P., Seinfeld,~J H., and Saxena,~P.: Atmospheric gas aerosol equilibrium, II: analysis of common approximations and activity coefficient calculation methods, Aerosol Sci. Technol. 19, 182–198, 1993b.

Kim,~Y P. and Seinfeld,~J H.: Atmospheric gas-aerosol equilibrium III: thermo-dynamics of crustal elements \chemCa^2+, \chemK^+, and \chemMg^2+, Aerosol Sci. Technol., 22, 93–110, 1995.

Kouvarakis,~G. and Mihalopouls,~N.: Seasonal variation of dimethylsulfide in the gas phase and of methanesulfonate and non-sea-salt sulfate in the aerosol phase measured in the Eastern Mediterranean atmosphere, Atmos. Environ., 36, 929–938, 2002.

Lelieveld,~J., Berresheim,~H., Borrmann,~S., Crutzen,~P J., Dentener,~F J., Fischer,~H., Feichter,~J., Flatau,~P J., Heland,~J., Holzinger,~R., Korrmann,~R., Lawrence,~M G., Levin,~Z., Markowicz,~K M., Mihalopoulos, ~N., Minikin,~A., Ramanathan,~V., de Reus,~M., Roelofs,~G J., Scheeren,~H. ~A., Sciare,~J., Schlager,~H., Schultz,~M., Siegmund,~P., Steil,~B., Stephanou,~E G., Stier,~P., Traub,~M., Warneke,~C., Williams,~J., and Ziereis,~H.: Global air pollution crossroads over the Mediterranean, Science, 298, 794–799, 2002.

Liao,~H., Adams,~P J., Chung,~S H., Seinfeld,~J H., Mickley,~L J. and Jacob, ~D J.: Interactions between tropospheric chemistry and aerosols in a~unified general circulation model, J. Geophys. Res., 108(D1), 4001, doi:10.1029/2001JD001260, 2003.

Markar,~P A., Bouchet,~V S., and Nenes,~A.: Inorganic chemistry calculations using HETV – a~vectorized solver for the \chemSO_4^2-\chemNO_3^-\chemNH_4^+ system based on the ISORROPIA algorithms, Atmos. Environ., 37, 2279–2294, doi:10.1016/S1352–2310(03)00074–8.510, 2003.

Meng,~Z., Seinfeld,~J H., Saxena,~P., and Kim,~Y P.: Atmospheric gas-aerosol equilibrium, IV: thermodynamics of carbonates, Aerosol Sci. Technol., 23, 131–154, 1995.

Meng,~Z. and Seinfeld,~J H.: Time scales to achieve atmospheric gas-aerosol equilibrium for volatile species, Atmos. Environ., 30, 2889–2900, 1996.

Metzger,~S., Dentener,~F J., Lelieveld,~J., and Pandis,~S N.: Gas/aerosol partitioning I: A~computationally efficient model, J. Geophys. Res., 107(D16), ACH 16-1-24, doi:10.1029/2001JD001102, 2002.

Metzger, S., Mihalopoulos, N., and Lelieveld, J.: Importance of mineral cations and organics in gas-aerosol partitioning of reactive nitrogen compounds: case study based on MINOS results, Atmos. Chem. Phys., 6, 2549–2567, 2006.

Metzger, S. and Lelieveld, J.: Reformulating atmospheric aerosol thermodynamics and hygroscopic growth into fog, haze and clouds, Atmos. Chem. Phys., 7, 3163–3193, 2007.

Moya,~M., Ansari,~A S., and Pandis,~S N.: Partitioning of nitrate and ammonium between the gas and particulate phases during the 1997 IMADA-AVER study in Mexico City, Atmos. Environ., 35, 1791–1804, 2001.

Nenes,~A., Pilinis,~C., and Pandis,~S N.: ISORROPIA: a~new thermodynamic equilibrium model for multiphase multicomponent marine aerosols, Aquatic Geochem., 4, 123–152, 1998.

Nenes,~A., Pilinis,~C., and Pandis,~S N.: Continued development and testing of a~new thermodynamic aerosol module for urban and regional air quality models, Atmos. Environ., 33, 1553–1560, 1999.

Penner,~J E., Chuang,~C C., and Grant,~K.: Climate forcing by carbonaceous and sulfate aerosols, Clim. Dym., 14, 839–851, 1998.

Pilinis,~C. and Seinfeld,~J H.: Continued development of a~general equilibrium model for inorganic multicomponent atmospheric aerosols, Atmos. Environ., 32, 2453–2466, 1987.

Pilinis,~C., Pandis,~S N., and Seinfeld,~J H.: Sensitivity of direct climate forcing by atmospheric aerosols to aerosol size and composition, J. Geophys. Res., 100, 18739–18754, 1995.

Pitzer,~K S. and Mayorga,~G.: Thermodynamics of electrolytes, II, Activity and osmotic coefficients for strong electrolytes with one or both ions univalent, J. Phys. Chem., 77, 2300–2308, 1973.

Salisbury, G., Williams, J., Holzinger, R., Gros, V., Mihalopoulos, N., Vrekoussis, M., Sarda-Estève, R., Berresheim, H., von Kuhlmann, R., Lawrence, M., and Lelieveld, J.: Ground-based PTR-MS measurements of reactive organic compounds during the MINOS campaign in Crete, July–August 2001, Atmos. Chem. Phys., 3, 925–940, 2003.

Saxena,~P., Seigneur,~C., Hudischewskyj,~A B., and Seinfeld,~J H.: A~comparative study of equilibrium approaches to the chemical characterizations of secondary aerosols, Atmos. Environ., 20, 1471–1484, 1986.

Seinfeld,~J H. and Pandis,~S N.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John, Wiley & Sons, Inc., 1998.

Spann,~J F. and Richardson,~C B.: Measurement of the water cycle in mixed ammonium acid sulfate particles, Atmos. Environ., 19(5), 819–825, 1985.

Stokes,~R H. and Robinson,~R A.: Interactions in aqueous nonelectrolyte solutions,~I. Solute-solvent equilibria, J. Phys. Chem., 70, 2126–2130, 1966.

Topping, D. O., McFiggans, G. B., and Coe, H.: A curved multi-component aerosol hygroscopicity model framework: Part 2 – Including organic compounds, Atmos. Chem. Phys., 5, 1223–1242, 2005.

Yu,~S., Dennis,~R., Roselle,~S., Nenes,~A., Walker,~J., Eder,~B., Schere, ~K., Swall,~J., and Robarge,~W.: An assessment of the ability of three-dimensional air quality models with current thermodynamic equilibrium models to predict aerosol \chemNO_3^-, J. Geophys. Res., 110, D07S13, doi:10.1029/2004JD004718, 2005.

Wexler,~A S. and Clegg,~S L.: Atmospheric aerosol models for systems including the ions \chemH^+, \chemNH_4^+, \chemNa^+, \chemSO_4^2-, \chemNO_3^-, \chemCl^-, \chemBr^- and \chemH_2O, J. Geophys. Res., 107(D14), 4207, doi:10.1029/2001JD000451.593, 2002.

Wexler,~A S. and Seinfeld,~J H.: The distribution of ammonium salts among a~size and composition dispersed aerosol. Atmos. Environ., 24A, 1231–1246, 1990.

Wexler,~A S. and Seinfeld,~J H.: Second-generation inorganic aerosol model. Atmos. Environ., 25A, 2731–2748, 1991.

Zaveri,~R A., Easter,~R C., and Peters,~L K.: A~computationally efficient Multicomponent Equilibrium Solver for Aerosols (MESA), J. Geophys. Res., 110, D24203, doi:10.1029/2004JD005618, 2005.

Zhang,~Y., Seigneur,~C., Seinfeld, J~H., Jacobson,~M Z., Clegg,~S L., and Binkowski,~F.: A~comparative review of inorganic aerosol thermodynamic equilibrium modules: similarities, differences, and their likely causes, Atmos. Environ., 34, 117–137, 2000.