Atmospheric Chemistry and Physics Discussions
www.atmos-chem-phys-discuss.net
1680-7367
1680-7375
6
6
2006
10.5194/acpd-6-12503-2006
http://www.atmos-chem-phys-discuss.net/6/12503/2006/
http://www.atmos-chem-phys-discuss.net/6/12503/2006/acpd-6-12503-2006.html
http://www.atmos-chem-phys-discuss.net/6/12503/2006/acpd-6-12503-2006.pdf
12503
12548
2006-12-05
Closure between measured and modelled particle hygroscopic growth during TORCH2 implies ammonium nitrate artefact in the HTDMA measurements
M. Gysel
martin.gysel@psi.ch
J. Crosier
D. O. Topping
J. D. Whitehead
K. N. Bower
M. J. Cubison
P. I. Williams
M. J. Flynn
G. B. McFiggans
H. Coe
Atmospheric Sciences Group, SEAES, University of Manchester, P.O. Box 88, Manchester, M60 1QD, UK
Labor für Atmsphärenchemie, Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
now at: Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO 80309, USA
Measurements of aerosol properties were made in aged polluted and clean background air masses encountered at the North
Norfolk (UK) coastline during the second field campaign of the Tropospheric ORganic CHemistry project (TORCH2) in May
2004. Hygroscopic growth factor (GF) measurements were performed at 90% relative humidity (RH) for
<i>D</i><sub>0</sub>=27–217 nm particles using a Hygroscopicity Tandem Differential Mobility Analyser (HTDMA), while the
aerosol composition was simultaneously measured with an Aerodyne aerosol mass spectrometer (Q-AMS). During the clean
background events the aerosol was characterised by little size dependence of properties with generally large GFs and
inorganic sulphate being the dominant compound. In aged polluted air masses the particles were dominated by inorganic
sulphate and nitrate at larger sizes, whereas organics were the largest fraction in smaller particles, thus explaining
the trend of smaller GFs at smaller sizes. Organics do contribute to the hygroscopic growth, particularly at small
sizes, but generally the dominant contribution to growth at 90% RH comes from inorganic salts. The ZSR mixing rule
was used to predict GFs based on the chemical composition, theoretical GFs of pure inorganic salts and a "bulk" GF of
~1.20 for the organics. Good quantitative closure with HTDMA measurements as a function of both particle size and
time was achieved in the absence of nitrate. However, GFs were clearly overpredicted at times when a significant
fraction of nitrate was present. After careful considerations we attribute the overprediction to substantial
evaporation losses of ammonium nitrate in the HTDMA instrument. If true, this implies that the ZSR predictions based on
composition might be more representative of the actual "bulk" behaviour of undisturbed ambient particles than the HTDMA
measurements.
<br><br>
The simplified model approach using the ZSR rule and a constant organic growth factor made high size and time
resolution possible, which has proven to be essential for a valid closure study. The ZSR mixing rule appears to be
sufficiently accurate, as the GF predictions are more sensitive to the exact GFs of the inorganic compounds than to the
growth factor of the moderately hygroscopic organics. Therefore a more detailed analysis and modelling of the organic
fraction at the expense of time and size resolution is not worth the effort for an aged aerosol and discrepancies in
either direction might even be cancelled out by averaging.
Aklilu, Y., Mozurkewich, M., Prenni, A J., Kreidenweis, S M., Alfarra, M R., Allan, J D., Anlauf, K., Brook, J., Leaitch, W R., Sharma, S., Boudries, H., and Worsnop, D R.: Hygroscopicity of particles at two rural, urban influenced sites during Pacific 2001: Comparison with estimates of water uptake from particle composition, Atmos. Env., 40, 2650–2661, 2006.
Alfarra, M R., Coe, H., Allan, J D., Bower, K N., Boudries, H., Canagaratna, M R., Jimenez, J L., Jayne, J T., Garforth, A A., Li, S M., and Worsnop, D R.: Characterization of urban and rural organic particulate in the lower Fraser valley using two aerodyne aerosol mass spectrometers, Atmos. Env., 38, 5745–5758, 2004.
Alfarra, M R., Paulsen, D., Gysel, M., Garforth, A A., Dommen, J., Prév\^ot, A. S H., Worsnop, D R., Baltensperger, U., and Coe, H.: A mass spectrometric study of secondary organic aerosols formed from the photooxidation of anthropogenic and biogenic precursors in a reaction chamber, Atmos. Chem. Phys., 6, 5279–5293, 2006.
Allan, J D., Jimenez, J L., Williams, P I., Alfarra, M R., Bower, K N., Jayne, J T., Coe, H., and Worsnop, D R.: Quantitative sampling using an Aerodyne aerosol mass spectrometer 1. Techniques of data interpretation and error analysis, J. Geophys. Res, 108, 4090, doi:10.1029/2002JD002 358, 2003.
Allan, J D., Bower, K N., Coe, H., Boudries, H., Jayne, J T., Canagaratna, M R., Millet, D B., Goldstein, A H., Quinn, P K., Weber, R J., and Worsnop, D R.: Submicron aerosol composition at Trinidad Head, California, during ITCT 2K2: Its relationship with gas phase volatile organic carbon and assessment of instrument performance, J. Geophys. Res, 109, 2004.
Baltensperger, U., Kalberer, M., Dommen, J., Paulsen, D., Alfarra, M R., Coe, H., Fisseha, R., Gascho, A., Gysel, M., Nyeki, S., Sax, M., Steinbacher, M., Prevot, A. S H., Sjögren, S., Weingartner, E., and Zenobi, R.: Secondary organic aerosols from anthropogenic and biogenic precursors, Faraday Discuss., 130, 265–278, 2005.
Berg, O H., Swietlicki, E., Frank, G., Martinsson, B G., Cederfelt, S I., Laj, P., Ricci, L., Berner, A., Dusek, U., Galambos, Z., Mesfin, N., Yuskiewicz, B., Wiedensohler, A., Stratmann, F., and Orsini, D.: Comparison of observed and modeled hygroscopic behavior of atmospheric particles, Contr. Atmos. Phys., 71, 47–64, 1998.
Canagaratna, M R., Jayne, J T., Jimenez, J L., Allan, J D., Alfarra, M R., Zhang, Q., Onasch, T B., Drewnick, F., Coe, H., Middlebrook, A., Delia, A., Williams, L R., Trimborn, A M., Northway, M J., Kolb, C E., Davidovits, P., and Worsnop, D R.: Chemical and microphysical characterization of ambient aerosols with the Aerodyne aerosol mass spectrometer, Mass Spec. Rev., in press, 2006.
Carrico, C M., Kreidenweis, S M., Malm, W C., Day, D E., Lee, T., Carrillo, J., McMeeking, G R., and Collett~Jr., J L.: Hygroscopic growth behavior of a carbon-dominated aerosol in Yosemite National Park, Atmos. Env., 39, 1393–1404, 2005.
Chan, M N. and Chan, C K.: Mass transfer effects in hygroscopic measurements of aerosol particles, Atmos. Chem. Phys., 5, 2703–2712, 2005.
Clegg, S L. and Pitzer, K S.: Thermodynamics of multicomponent, miscible, ionic-solutions: generalized equations for symmetrical electrolytes, J. Phys. Chem., 96, 3513–3520, 1992.
Clegg, S L., Pitzer, K S., and Brimblecombe, P.: Thermodynamics of multicomponent, miscible, ionic solutions. 2. Mixtures including unsymmetrical electrolytes, J. Phys. Chem., 96, 9470–9479, 1992. %
%Crosier, J., Allan, J D., Coe, H., Bower, K N., Formenti, P., and Williams, % P I.: Chemical composition of summertime aerosol in the Po Valley (Italy), % Northern Adriatic and Black Sea, Quart. J. Roy. Meteorol. Soc., submitted\blackbox\bf status?, % 2006.
Cubison, M., Coe, H., and Gysel, M.: Retrieval of hygroscopic tandem DMA measurements using an optimal estimation method., J. Aerosol Sci., 36, 846–865, 2005.
Dassios, K G. and Pandis, S N.: The mass accommodation coefficient of ammonium nitrate aerosol, Atmos. Env., 33, 2993–3003, 1999.
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, 1471–1479, 2000.
Dinar, E., Mentel, T F., and Rudich, Y.: The density of humic acids and humic like substances (HULIS) from fresh and aged wood burning and pollution aerosol particles, Atmos. Chem. Phys., 6, 5213–5224, 2006.
Fredenslund, A., Jones, R L., and Prausnitz, J M.: Group-contribution estimation of activity-coefficients in nonideal liquid-mixtures, Aiche J., 21, 1086–1099, 1975.
Gysel, M., Weingartner, E., and Baltensperger, U.: Hygroscopicity of aerosol particles at low temperatures. 2. Theoretical and experimental hygroscopic properties of laboratory generated aerosols, Env. Sci. Tech., 36, 63–68, 2002.
Gysel, M., Nyeki, S., Paulsen, D., Weingartner, E., Baltensperger, U., Galambos, I., and Kiss, G.: Hygroscopic properties of water-soluble matter and humic-like organics in atmospheric fine aerosol, Atmos. Chem. Phys., 4, 35–50, 2004.
Hämeri, K., Charlson, R., and Hansson, H C.: Hygroscopic properties of mixed ammonium sulfate and carboxylic acids particles, Aiche J., 48, 1309–1316, 2002.
Hand, J L., Kreidenweis, S M., Sherman, D E., Collett, J L., Hering, S V., Day, D E., and Malm, W C.: Aerosol size distributions and visibility estimates during the Big Bend regional aerosol and visibility observational (BRAVO) study, Atmos. Env., 36, 5043–5055, 2002.
Jayne, J T., Leard, D C., Zhang, X F., Davidovits, P., Smith, K A., Kolb, C E., and Worsnop, D R.: Development of an aerosol mass spectrometer for size and composition analysis of submicron particles, Aerosol Sci. Tech., 33, 49–70, 2000.
Jimenez, J L., Jayne, J T., Shi, Q., Kolb, C E., Worsnop, D R., Yourshaw, I., Seinfeld, J H., Flagan, R C., Zhang, X F., Smith, K A., Morris, J W., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer, J. Geophys. Res., 108, 8425, doi:10.1029/2001JD001213, 2003.
Johnson, G R., Ristovski, Z D., D'Anna, B., and Morawska, L.: Hygroscopic behavior of partially volatilized coastal marine aerosols using the volatilization and humidification tandem differential mobility analyzer technique, J. Geophys. Res., 110, D20203, doi:10.1029/2004JD005657, 2005.
Kay, M J. and Box, M.: Radiative effects of absorbing aerosols and the impact of water vapor, J. Geophys. Res, 105, 12 221–12 234, 2000.
Kreidenweis, S M., Koehler, K., DeMott, P J., Prenni, A J., Carrico, C., and Ervens, B.: Water activity and activation diameters from hygroscopicity data – Part I: Theory and application to inorganic salts, Atmos. Chem. Phys., 5, 1357–1370, 2005.
Krivácsy, Z., Hoffer, A., Sárvári, Z., Temesi, D., Baltensperger, U., Nyeki, S., Weingartner, E., Kleefeld, S., and Jennings, S G.: Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites, Atmos. Env., 35, 6231–6244, 2001.
Marcolli, C. and Krieger, U K.: Phase changes during hygroscopic cycles of mixed organic/inorganic model systems of tropospheric aerosols, J. Phys. Chem., A110, 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., A108, 2216–2224, 2004.
McFiggans, G., Alfarra, M R., Allan, J., Bower, K., Coe, H., Cubison, M., Topping, D., Williams, P., Decesari, S., Facchini, C., and Fuzzi, S.: Simplification of the representation of the organic component of atmospheric particulates, Faraday Discuss., 130, 341–362, 2005.
McFiggans, G., Artaxo, P., Baltensperger, U., Coe, H., Facchini, M., Feingold, G., Fuzzi, S., Gysel, M., Laaksonen, A., Lohmann, U., Mentel, T., Murphy, D., O'Dowd, C., Snider, J., and Weingartner, E.: The effect of physical and chemical aerosol properties on warm cloud droplet activation, Atmos. Chem. Phys., 6, 2593–2649, 2006.
Mikhailov, E., Vlasenko, S., Niessner, R., and Pöschl, U.: Interaction of aerosol particles composed of protein and salts with water vapor: hygroscopic growth and microstructural rearrangement, Atmos. Chem. Phys., 4, 323–350, 2004.
Ming, Y. and Russell, L M.: Thermodynamic equilibrium of organic-electrolyte mixtures in aerosol particles, Aiche J., 48, 1331–1348, 2002.
Peng, C., Chan, M N., and Chan, C K.: The hygroscopic properties of dicarboxylic and multifunctional acids: Measurements and UNIFAC predictions, Env. Sci. Tech., 35, 4495–4501, 2001.
Poling, B E., Prausnitz, J M., and O'Connell, J P.: The Properties of Gases and Liquids, McGraw-Hill, New York, 5 edn., 2001.
Putaud, J P., Raes, F., Van~Dingenen, R., Brüggemann, E., Facchini, M C., Decesari, S., Fuzzi, S., Gehrig, R., Hüglin, C., Laj, P., Lorbeer, G., Maenhaut, W., Mihalopoulos, N., Mülller, K., Querol, X., Rodriguez, S., Schneider, J., Spindler, G., ten Brink, H., Tørseth, K., and Wiedensohler, A.: European aerosol phenomenology-2: chemical characteristics of particulate matter at kerbside, urban, rural and background sites in Europe, Atmos. Env., 38, 2579–2595, 2004.
Ramanathan, V., Crutzen, P J., Kiehl, J T., and Rosenfeld, D.: Aerosols, climate, and the hydrological cycle, Science, 294, 2119–2124, 2001.
Saxena, P., Hildemann, L M., McMurry, P H., and Seinfeld, J H.: Organics alter hygroscopic behavior of atmospheric particles, J. Geophys. Res., 100, 18 755–18 770, 1995.
Seinfeld, J H. and Pandis, S N.: Atmospheric Chemistry and Physics. From Air Pollution to Climate Change, John Wiley & Sons, Inc., New York, pp. 531 ff., 1998.
Sjogren, S., Gysel, M., Weingartner, E., Baltensperger, U., Cubison, M., Coe, H., Zardini, A., Marcolli, C., Krieger, U., 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., accepted, 2006.
Stokes, R H. and Robinson, R A.: Interactions in aqueous nonelectrolyte solutions. I. Solute-solvent equilibria, J. Phys. Chem., 70, 2126–2130, 1966.
Swietlicki, E., Zhou, J C., Berg, O H., Martinsson, B G., Frank, G., Cederfelt, S I., Dusek, U., Berner, A., Birmili, W., Wiedensohler, A., Yuskiewicz, B., and Bower, K N.: A closure study of sub-micrometer aerosol particle hygroscopic behaviour, Atmos. Res., 50, 205–240, 1999.
Topping, D O., McFiggans, G B., and Coe, H.: A curved multi-component aerosol hygroscopicity model framework: Part 1 - Inorganic compounds, Atmos. Chem. Phys., 5, 1205–1222, 2005a.
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, 2005b.
Vlasenko, A., Sjögren, S., Weingartner, E., Gäggeler, H W., and Ammann, M.: Generation of submicron Arizona test dust aerosol: Chemical and hygroscopic properties, Aerosol Sci. Tech., 39, 452–460, 2005.
Weingartner, E., Burtscher, H., and Baltensperger, U.: Hygroscopic properties of carbon and diesel soot particles, Atmos. Env., 31, 2311–2327, 1997.
Weingartner, E., Sjögren, S., Cozic, J., Verheggen, B., Baltensperger, U., Alfarra, M R., Bower, K N., Flynn, M J., Gysel, M., and Coe, H.: Hygroscopic properties and chemical composition of aerosol particles at the high alpine site Jungfraujoch, J. Aerosol Sci., 35, S135–S136, 2004.
Winkelmayr, W., Reischl, G P., Lindner, A O., and Berner, A.: A new electromobility spectrometer for the measurement of aerosol size distributions in the size range from 1 to 1000 nm, J. Aerosol Sci., 22, 289–296, 1991.
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, 4638, doi:10.1029/2003JD003775, 2003.
Zdanovskii, A.: New methods for calculating solubilities of electrolytes in multicomponent systems, Zhur. Fiz. Khim., 22, 1475–1485, 1948.
Zhang, Q., Alfarra, M R., Worsnop, D R., Allan, J D., Coe, H., Canagaratna, M R., and Jimenez, J L.: Deconvolution and quantification of hydrocarbon-like and oxygenated organic aerosols based on aerosol mass spectrometry, Env. Sci. Tech., 39, 4938–4952, 2005a.
Zhang, Q., Worsnop, D R., Canagaratna, M R., and Jimenez, J L.: Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols, Atmos. Chem. Phys., 5, 3289–3311, 2005b.