Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
8
2
2008
10.5194/acpd-8-5235-2008
http://www.atmos-chem-phys-discuss.net/8/5235/2008/
http://www.atmos-chem-phys-discuss.net/8/5235/2008/acpd-8-5235-2008.html
http://www.atmos-chem-phys-discuss.net/8/5235/2008/acpd-8-5235-2008.pdf
5235
5268
2008-03-12
A combined particle trap/HTDMA hygroscopicity study of mixed inorganic/organic aerosol particles
A. A. Zardini
S. Sjogren
C. Marcolli
U. K. Krieger
M. Gysel
E. Weingartner
U. Baltensperger
T. Peter
Institute for Atmospheric and Climate Science, ETH, CH-8092 Zurich, Switzerland
Laboratory of Atmospheric Chemistry, Paul Scherrer Institut, CH-5232 Villigen, Switzerland
Atmospheric aerosols are often mixtures of inorganic
and organic material. Organics can represent a large fraction of the total aerosol mass
and are comprised of water-soluble and insoluble compounds.
Increasing attention was paid in the last decade
to the capability of mixed inorganic/organic aerosol particles
to take up water (hygroscopicity).
We performed hygroscopicity measurements
of internally mixed particles containing ammonium sulfate and carboxylic acids
(citric, glutaric, adipic acid)
in parallel with an electrodynamic balance (EDB)
and a hygroscopicity tandem differential mobility analyzer (HTDMA).
The organic compounds were chosen to represent three distinct physical states.
During hygroscopicity cycles covering hydration and dehydration
measured by the EDB and the HTDMA,
pure citric acid remained always liquid,
adipic acid remained always solid,
while glutaric acid could be either.
We show that the hygroscopicity of mixtures of the above compounds is well described
by the Zdanovskii-Stokes-Robinson (ZSR) relationship as long as the two-component particle is completely liquid
in the ammonium sulfate/citric acid and in the ammonium sulfate/glutaric acid cases.
However, we observe significant discrepancies compared to what is expected from bulk thermodynamics
when a solid component is present.
We explain this in terms of a complex morphology resulting
from the crystallization process leading to veins, pores,
and grain boundaries which allow for water sorption in excess
of bulk thermodynamic predictions caused by the inverse Kelvin effect on concave surfaces.
Apelblat, A., Dov, M., Wisniak, J., and Zabicky, J.: Osmotic and Activity Coefficients of HO2CCH2C(OH)(CO2H)CH2CO2H (Citric Acid) in Concentrated Aqueous Solutions at Temperatures from 298.15 K to 318.15 K, J. Chem. Thermodynamics, 27, 347–353, 1995.
Braban C. F. and Abbatt, J. P. D.: A study of the phase transition behavior of internally mixed ammonium sulfate – malonic acid aerosols, Atmos. Chem. Phys., 4, 1451–1459, 2004.
Brooks, S. D., Wise, M. E., Cushing, M., and Tolbert, M. A.: Deliquescence behavior of organic/ammonium sulfate aerosol, Geophys. Res. Lett., 29(19), 1917, 2002.
Camuffo, D.: Condensation–Evaporation cycles in pore and capillary systems according to the Kelvin model, Water, Air, and Soil Pollution, 21, 151–159, 1984.
Chan, C. K., Flagan, R. C., and Seinfeld, J. H.: Water activities of NH4NO3(NH4)2SO4 solutions. Atmos. Environ., 26, 1661–1673, 1992.
Chan, M. N. and Chan, C. K.: Mass transfer effects in hygroscopic measurements of aerosol particles, Atmos. Chem. Phys., 5, 2703–2712, 2005.
Choi, M. Y. and Chan, C. K.: The Effects of Organic Species on the Hygroscopic Behaviors of Inorganic Aerosols, Environ. Sci. Technol., 36, 11, 2422–2428, 2002.
Clegg, S. L., Brimblecombe, P., and Wexler, A. S.: A thermodynamic model of the system H+ – NH4+ – SO42 – – NO3 – – H2O at tropospheric temperatures, J. Phys. Chem. A, 102, 2137–2154, 1998.
Cruz, C. N. and Pandis, S. N.: Deliquescence and Hygroscopic Growth of Mixed Inorganic-Organic Atmospheric Aerosol, Environ. Sci. Technol., 34(20), 4313–4319, 2000.
Davis, E. J. and Periasamy, R.: Light-scattering and aerodynamic size measurements for homogeneous and inhomogeneous microspheres, Langmuir, 1, 373–379, 1985.
Davis, E. J., Buehler, M. F., and Ward, T. L.: The double-ring electrodynamic balance for microparticle characterization, Rev. Sci. Instrum., 61, 1281–1288, 1990.
Dick, W. D., Saxena, P., and McMurry, P. H.: Estimation of water uptake by organic compounds in submicron aerosols measured during the Southeastern Aerosol and Visibility Study, J. Geophys. Res., 105(D1), 1471–1479, 2000.
Fuzzi, S., Andreae, M. O., Huebert, B. J., Kulmala, M., Bond, T. C., Boy, M., Doherty, S., J., Guenther, A., Kanakidou, M., Kawamura, K., Kerminen, V M., Lohmann, U., Russell, L. M., and Pöschl, U.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, 2006.
Gysel, M., Weingartner, E., Nyeki, S., Paulsen, D., Baltensperger, U., Galambos, I. et al.: Hygroscopic properties of water-soluble matter and humic-like organics in atmospheric fine aerosol, Atmos. Chem. Phys., 4, 35–50, 2004.
Hameri, K., Charlson, R., and Hansson, H. C.: Hygroscopic Properties of Mixed Ammonium Sulfate and Carboxylic Acids Particles, AIChE Journal, 48, 6, 1309–1316, 2002.
Intergovernmental Panel on Climate Change (IPCC): Fourth Assessment Report, Working Group I Report "The Physical Science Basis", Chapter 2, http://www.ipcc.ch/, 2007.
Jacobson, M. C., Hansson, H. C., Noone, K. J., and Charlson, R. J.: Organic atmospheric aerosols: Review and state of science, Rev. Geophys., 38(2), 267–294, 2000.
Kanakidou, M., Seinfeld, J H., Pandis, S. N. et al.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005.
Krieger, U. K, Colberg, A. C., Weers, U., Koop, T., and Peter, Th.: Supercooling of single H<sub>2</sub>SO<sub>4</sub>/H<sub>2</sub>O aerosols to 158 K: no evidence for the occurrence of the octahydrate, Geophys. Res. Lett., 27, 2097–2100, 2000.
Krieger, U., K., Braun, C.: Light-scattering intensity fluctuations in single aerosol particles during deliquescence, J. Quant. Spectrosc. Radiat. Transfer, 70, 545–554, 2001.
Levien, B. J.: A Physicochemical Study of Aqueous Citric Acid Solutions, J. Phys. Chem., 59, 640–644, 1955.
Marcolli, C., and Krieger, U. K.: Phase Changes during Hygroscopic Cycles of Mixed Organic/Inorganic Model Systems of Tropospheric Aerosols, J. Phys. Chem. A., 110, 1881–1893, 2006.
Marcolli, C., Luo, B., and Peter, T.: Mixing of the organic aerosol fractions: liquids as the thermodynamically stable phases, J. Phys. Chem. A., 108, 2216–2224, 2004.
Middlebrook, A. M., Murphy, D. M., and Thomson, D. S.: Observations of organic material in individual marine particles at Cape Grim during the First Aerosol Characterization Experiment (ACE 1), J. Geophys. Res., 103(D13), 16 475–16 483, 1998.
Murphy, D. M., Cziczo, D. J., Froyd, K. D., et al.: Single-particle mass spectrometry of tropospheric aerosol particles, J. Geophys. Res., 111, D23S32, 2006.
Pant, A., Fok, A., Parson, M. T., Mak J., and Bertram, A. K.: Deliquescence and crystallization of ammonium sulfate-glutaric acid and sodium chloride-glutaric acid particles, Geophys. Res. Lett, 31, L12111, doi:10.1029/2004GL020025, 2004.
Peng, C.; Chan, M. N., and Chan, C. K.: The Hygroscopic Properties of Dicarboxylic and Multifunctional Acids: Measurements and UNIFAC Predictions, Environ. Sci. Technol., 35, 4495–4501, 2001.
Prenni, A. J., De Mott, P. J., and Kreidenweis, S. M.: Water uptake of internally mixed particles containing ammonium sulfate and dicarboxylic acids, Atmos. Environ., 37 (30), 4243–4251, 2003.
Price, P. B.: A habitat for psychrophiles in deep Antarctic ice, PNAS, 97 (3),1247–1251, 2000.
Richardson, C. B.: A stabilizer for single microscopic particles in a quadrupole trap, Rev. Sci. Instrum., 61, 1334–1335, 1990.
Rogge, W. F., Mazurek, M. A., Hildemann, L. M., and Cass, G. R.: Quantification of urban organic aerosols at a molecular level: identification, abundance and seasonal variation, Atmos. Environ., 27A, 8, 1309–1330, 1993.
Saxena, P., Hildemann, L. M., McMurry, P. H., and Seinfeld, J. H. J.: Organics alter hygroscopic behaviour of atmospheric particles, J. Geophys. Res., 100(D9), 18 755–18 770, 1995.
Semmler, M., Luo, B.P., Koop, T.: Densities of liquid H$^+$/NH$^+_4$/SO$_4^2-$/NO$^-_3$/H<sub>2</sub>O solutions at tropospheric temperatures, Atmos. Environ., 40, 467-483, 2006.
Sjogren, S., Gysel, M., Weingartner, E., Baltensperger, U., Cubison, M. J., Coe, H., Zardini, A. A., Marcolli, C., Krieger, U. K., and Peter, T.: Hygroscopic growth and water uptake kinetics of two-phase aerosol particles consisting of ammonium sulfate, adipic and humic acid mixtures, J. Aerosol Sci., 38, 157–171, 2007.
Stokes, R. H., and Robinson, R. A.: Interactions in aqueous nonelectrolyte solutions, solute-solvent equilibria, J. Phys. Chem., 70, 7, 2126–2131, 1966.
Svenningsson, B., Rissler, J., Swietlicki, E., Mircea, M., Bilde, M., Facchini, M. C., Decesari, S., Fuzzi, S., Zhou, J., M\o nster, J., and Rosen\o rn, T.: Hygroscopic growth and critical supersaturations for mixed aerosol particles of inorganic and organic compounds of atmospheric relevance, Atmos. Chem. Phys., 6, 1937–1952, 2006.
Thomson, W.: On the equilibrium of vapour at a curved surface of liquid, Phil. Mag. 42, 448–452, 1871.
Videen G., Pellegrino P., Ngo D., Videen, J., S., Pinnick, R., G.: Light-scattering intensity fluctuations in microdroplets containing inclusions. Appl. Opt., 36, 6115–6118, 1997.
Weingartner, E., Gysel, M., and Baltensperger, U.: Hygroscopicity of aerosol particles at low temperatures. 1. New low-temperature H-TDMA instrument: Setup and first applications, Env. Sci. Tech., 36, 1, 55–62, 2002.
Wise, M., E., Surratt, J., D., Curtis, D., B., Shilling, J., E., and Tolbert, M., A.: Hygroscopic growth of ammonium sulfate/dicarboxylic acids, J. Geophys. Res., 108 (D20), 4638, 2003.
Zdanovskii, A. B., Novyi metod rascheta rastvorimostei elektrolitov v mnogokomponentnykh sistemakh 1,2, Zh Fiz Khim., 22, 1486\textendash1495, 1478\textendash1485, 1948.