Atmospheric Chemistry and Physics
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2007
10.5194/acp-7-2313-2007
http://www.atmos-chem-phys.net/7/2313/2007/
http://www.atmos-chem-phys.net/7/2313/2007/acp-7-2313-2007.html
http://www.atmos-chem-phys.net/7/2313/2007/acp-7-2313-2007.pdf
2313
2337
2007-05-08
Secondary aerosol formation from atmospheric reactions of aliphatic amines
S. M. Murphy
A. Sorooshian
J. H. Kroll
N. L. Ng
P. Chhabra
C. Tong
J. D. Surratt
E. Knipping
R. C. Flagan
J. H. Seinfeld
seinfeld@caltech.edu
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA
Current Address: Aerodyne Research Inc., Billerica, MA, USA
Electric Power Research Institute, Palo Alto, CA, USA
Although aliphatic amines have been detected in
both urban and rural atmospheric aerosols, little is known about the
chemistry leading to particle formation or the potential aerosol yields from
reactions of gas-phase amines. We present here the first systematic study of
aerosol formation from the atmospheric reactions of amines. Based on
laboratory chamber experiments and theoretical calculations, we evaluate
aerosol formation from reaction of OH, ozone, and nitric acid with
trimethylamine, methylamine, triethylamine, diethylamine, ethylamine, and
ethanolamine. Entropies of formation for alkylammonium nitrate salts are
estimated by molecular dynamics calculations enabling us to estimate
equilibrium constants for the reactions of amines with nitric acid. Though
subject to significant uncertainty, the calculated dissociation equilibrium
constant for diethylammonium nitrate is found to be sufficiently small to
allow for its atmospheric formation, even in the presence of ammonia which
competes for available nitric acid. Experimental chamber studies indicate
that the dissociation equilibrium constant for triethylammonium nitrate is
of the same order of magnitude as that for ammonium nitrate. All amines
studied form aerosol when photooxidized in the presence of NO<sub>x</sub> with the
majority of the aerosol mass present at the peak of aerosol growth
consisting of aminium (R<sub>3</sub>NH<sup>+</sup>) nitrate salts, which repartition
back to the gas phase as the parent amine is consumed. Only the two tertiary
amines studied, trimethylamine and triethylamine, are found to form
significant non-salt organic aerosol when oxidized by OH or ozone;
calculated organic mass yields for the experiments conducted are similar for
ozonolysis (15% and 5% respectively) and photooxidation (23% and
8% respectively). The non-salt organic aerosol formed appears to be more
stable than the nitrate salts and does not quickly repartition back to the
gas phase.
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(D3), 4090, doi:10.1029/2002JD002358, 2003.
Allen, M., Evans, D. F., and Lumry, R.: Thermodynamic properties of the ethylammonium nitrate + water-system – partial molar volumes, heat-capacities, and expansivities, J. Solution. Chem., 14(8), 549–560, 1985.
Angelino, S., Suess, D. T., and Prather, K. A.: Formation of aerosol particles from reactions of secondary and tertiary alkylamines: Characterization by aerosol time-of-flight mass spectrometry, Environ. Sci. Technol., 35(15), 3130–3138, 2001.
Atkinson, R., Perry, R. A., and Pitts, J. N.: Rate constants for reactions of OH radical with (CH3)2NH, (CH3)3N, and C2H5NH2 over temperature range 298–426 degrees K, J. Chem. Phys., 68(4), 1850–1853, 1978.
Bahreini, R., Keywood, M. D., Ng, N. L., Varutbangkul, V., Gao, S., Flagan, R. C., Seinfeld, J. H., Worsnop, D. R., and Jimenez, J. L.: Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer, Environ. Sci. Technol., 39(15), 5674–5688, 2005.
Becke, A. D.: Density-functional thermochemistry III. The role of exact exchange, J Chem. Phys., 98(7), 5648–5652, 1993.
Beddows, D. C. S., Donovan, R. J., Harrison, R. M., Heal, M. R., Kinnersley, R. P., King, M. D., Nicholson, D. H., and Thompson, K. C.: Correlations in the chemical composition of rural background atmospheric aerosol in the UK determined in real time using time-of-flight mass spectrometry, J. Environ. Monit., 6(2), 124–133, 2004.
Cerius2, v. 4.0, Accelrys, San Diego, CA, 1999.
Chase, M. W.: NIST-JANAF themochemical tables, fourth edition, J. Phys. Chem. Ref. Data, Monograph 9, 1343–1290, 1998.
Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: State-of-the-art chamber facility for studying atmospheric aerosol chemistry, Environ. Sci. Technol., 35(12), 2594–2601, 2001.
Cottrell, T. L. and Gill, J. E.: The preparation and heats of combustion of some amine nitrates, J. Chem. Soc., (Jul), 1798–1800, 1951.
Cox, J. D., Harrop, D., and Head, A. J.: Standard enthalpy of formation of ammonium-nitrate and of the nitrate ion, J. Chem. Thermodyn., 11(8), 811–814, 1979.
DeCarlo, P. F., Slowik, J. G., Worsnop, D. R., Davidovits, P., and Jimenez, J. L.: Particle morphology and density characterization by combined mobility and aerodynamic diameter measurements. Part 1: Theory, Aerosol Sci. Technol., 38(12), 1185–1205, 2004.
Drewnick, F., Jayne, J. T., Canagaratna, M., Worsnop, D. R., and Demerjian, K. L.: Measurement of ambient aerosol composition during the PMTACS-NY 2001 using an aerosol mass spectrometer. Part II: Chemically speciated mass distributions, Aerosol Sci. Technol., 38, 104–117, 2004a.
Drewnick, F., Schwab, J. J., Jayne, J. T., Canagaratna, M., Worsnop, D. R., and Demerjian, K. L.: Measurement of ambient aerosol composition during the PMTACS-NY 2001 using an aerosol mass spectrometer. Part I: Mass concentrations, Aerosol Sci. Technol., 38, 92–103, 2004b.
Eichenau, W. and Liebsche, D.: Die molwarme des ammoniumnitrats zwischen 11 und 280 degrees K, Zeitschrift f\'ur Naturforschung Part a-Astrophysik Physik und Physikalische Chemie, A 20(1), 160, 1965.
Feibelman, P. J.: Force and total-energy calculations for a spatially compact adsorbate on an extended, metallic crystal surface, Phys. Rev. B, 35(6), 2626–2646, 1987.
Finlayson-Pitts, B. J. and Pitts, J. N. J.: Atmospheric chemistry : Fundamentals and experimental techniques, Wiley, New York, 1986.
Haar, L.: Thermodynamic properties of ammonia as an ideal gas, J. Res. Nbs. A. Phys. Ch., A 72(2), 207, 1968.
Hamoir, J., Nemmar, A., Halloy, D., Wirth, D., Vincke, G., Vanderplasschen, A., Nemery, B., and Gustin, P.: Effect of polystyrene particles on lung microvascular permeability in isolated perfused rabbit lungs: Role of size and surface properties, Toxicol. Appl. Pharmacol., 190(3), 278–285, 2003.
Herrmann, M., Engel, W., Schneider, J., and Goebel, H.: Rietveld refinement of the phase of NH4NO3 measured in-situ under different diffraction geometries, Materials Science Forum, 166, 489–494, 1994.
Huffman, J. A., Jayne, J. T., Drewnick, F., Aiken, A. C., Onasch, T., Worsnop, D. R., and Jimenez, J. L.: Design, modeling, optimization, and experimental tests of a particle beam width probe for the Aerodyne aerosol mass spectrometer, Aerosol Sci. Technol., 39(12), 1143–1163, 2005.
Jaguar, v. 6.5, Schrodinger, LLC, New York, NY, 2005.
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. Technol., 33(1–2), 49–70, 2000.
Kendall, R. A., Dunning Jr., T. H., and Harrison, R. J.: Electron affinities of the first-row atom revisited. Systematic basis sets and wave functions, J. Chem. Phys., 96(9), 6796–6806, 1992.
Keywood, M. D., Varutbangkul, V., Bahreini, R., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from the ozonolysis of cycloalkenes and related compounds, Environ. Sci. Technol., 38(15), 4157–4164, 2004.
Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from isoprene photooxidation, Environ. Sci. Technol., 40(6), 1869–1877, 2006.
Lin, S.-T., Blanco, M., and Goddard III, W. A.: The two-phase model for calculating thermodynamic properties of liquids from molecular dynamics: Validation for the phase diagram of Lennard-Jones fluids, J. Chem. Phys., 119(22), 11 792–11 805, 2003.
Mace, K. A., Artaxo, P., and Duce, R. A.: Water-soluble organic nitrogen in Amazon basin aerosols during the dry (biomass burning) and wet seasons, J. Geophys. Res., 108(D16), 4512, doi:10.1029/2003JD003557, 2003.
Makela, J. M., Yli-Koivisto, S., Hiltunen, V., Seidl, W., Swietlicki, E., Teinila, K., Sillanpaa, M., Koponen, I. K., Paatero, J., Rosman, K., and Hameri, K.: Chemical composition of aerosol during particle formation events in boreal forest, Tellus B, 53(4), 380–393, 2001.
McGregor, K. G. and Anastasio, C.: Chemistry of fog waters in California's central valley: 2. Photochemical transformations of amino acids and alkyl amines, Atmos. Environ., 35(6), 1091–1104, 2001.
Mozurkewich, M.: The dissociation-constant of ammonium-nitrate and its dependence on temperature, relative-humidity and particle-size, Atmos. Environ. A-Gen., 27(2), 261–270, 1993.
Murphy, D. M. and Thomson, D. S.: Chemical composition of single aerosol particles at idaho hill: Positive ion measurements, J. Geophys. Res., 102(D5), 6341–6352, 1997.
Mylrajan, M., Srinivasan, T. K. K., and Sreenivasamurthy, G.: Crystal structure of monomethylammonium nitrate, J Cryst. Spectrosc., 15(5), 493–500, 1985.
Neff, J. C., Holland, E. A., Dentener, F. J., McDowell, W. H., and Russell, K. M.: The origin, composition and rates of organic nitrogen deposition: A missing piece of the nitrogen cycle?, Biogeochemistry, 57(1), 99–136, 2002.
Nemmar, A., Hoylaerts, M. F., Hoet, P. H. M., Dinsdale, D., Smith, T., Xu, H. Y., Vermylen, J., Nemery, B., and Nemery, B.: Ultrafine particles affect experimental thrombosis in an in vivo hamster model, Am. J. Resp. Crit. Care., 166(7), 998–1004, 2002.
Ngwabie, N. M. and Hintz, T.: Mxing ratio measurements and flux estimates of volatile organic compounds (voc) from a cowshed with conventional manure treatment indicate significant emmissions to the atmosphere, Geograph. Res. Abstr., 7(01175), 2005.
Perry, R. H., Green, D. W., and Maloney, J. O.: Perry's chemical engineers' handbook, McGraw-Hill, New York, 1997.
Pitts, J. N., Grosjean, D., Vancauwenberghe, K., Schmid, J. P., and Fitz, D. R.: Photo-oxidation of aliphatic-amines under simulated atmospheric conditions – formation of nitrosamines, nitramines, amides, and photo-chemical oxidant, Environ. Sci. Technol., 12(8), 946–953, 1978.
Rabaud, N. E., Ebeler, S. E., Ashbaugh, L. L., and Flocchini, R. G.: Characterization and quantification of odorous and non-odorous volatile organic compounds near a commercial dairy in California, Atmos. Environ., 37(7), 933–940, 2003.
Schade, G. W. and Crutzen, P. J.: Emission of aliphatic-amines from animal husbandry and their reactions – potential source of N2O and HCN, J. Atmos. Chem., 22(3), 319–346, 1995.
Schmitz, L. R., Chen, K. H., Labanowski, J., and Allinger, N. L.: Heats of formation of organic molecules calculated by density functional theory. III - amines, J. Phys. Org. Chem., 14(2), 90–96, 2001.
Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003.
Simoneit, B. R. T., Rushdi, A. I., Bin Abas, M. R., and Didyk, B. M.: Alkyl amides and nitriles as novel tracers for biomass burning, Environ. Sci. Technol., 37(1), 16–21, 2003.
Sorooshian, A., Brechtel, F. J., Ma, Y. L., Weber, R. J., Corless, A., Flagan, R. C., and Seinfeld, J. H.: Modeling and characterization of a particle-into-liquid sampler (pils), Aerosol Sci. Technol., 40(6), 396–409, 2006.
Stein, S. E.: Mass spectra by NIST mass spec data center, NIST chemistry webbook, NIST standard reference database number 69, Eds. Linstrom PJ, Mallard WG, National Institute of Standards and Technology, Gaithersburg MD, (http://webbook.nist.gov), 2005.
Stelson, A. W. and Seinfeld, J. H.: Relative-humidity and temperature-dependence of the ammonium-nitrate dissociation-constant, Atmos. Environ., 16(5), 983–992, 1982.
Surratt, J. D., Murphy, S. M., Kroll, J. H., Ng, N. L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R. C., and Seinfeld, J. H.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110(31), 9665–9690, 2006.
Tan, P. V., Evans, G. J., Tsai, J., Owega, S., Fila, M. S., and Malpica, O.: On-line analysis of urban particulate matter focusing on elevated wintertime aerosol concentrations, Environ. Sci. Technol., 36(16), 3512–3518, 2002.
Tuazon, E. C., Atkinson, R., Aschmann, S. M., and Arey, J.: Kinetics and products of the gas-phase reactions of O<sub>3</sub> with amines and related-compounds, Res. Chem. Intermed., 20(3–5), 303–320, 1994.
Verdozzi, C., Schultz, P. A., Wu, R., Edwards, A. H., and Kioussis, N.: Layer intermixing during metal/metal oxide adsorption: Ti/sapphire(0001), Phys. Rev. B, 66, 125 408, 2002.
Wagman, D. D., Evans, W. H., Parker, V. B., Halow, I., Bailey, S. M., and Schumm, R. H.: Selected values of chemical thermodynamic properties; tables for the first thirty-four elements in the standard order of arrangement, NBS Technical Note, 270(3), 1968.
Wagman, D. D., Evans, W. H., Parker, V. B., Schumm, R. H., Halow, I., Bailey, S. M., Churney, K. L., and Nuttall, R. L.: The nbs tables of chemical thermodynamic properties – selected values for inorganic and C-1 and C-2 organic-substances in si units, J. Phys. Chem. Ref. Data, 11(2), 91–110, 1982.
Weber, R. J., Orsini, D., Daun, Y., Lee, Y. N., Klotz, P. J., and Brechtel, F.: A particle-into-liquid collector for rapid measurement of aerosol bulk chemical composition, Aerosol Sci. Technol., 35(3), 718–727, 2001.
Yaws, C. L.: Yaws' handbook of thermodynamic and physical properties of chemical compounds, Knovel, 2003.
Zhang, Q. and Anastasio, C.: Free and combined amino compounds in atmospheric fine particles (pm2.5) and fog waters from northern California, Atmos. Environ., 37(16), 2247–2258, 2003.