Atmospheric Chemistry and Physics
www.atmos-chem-phys.net
1680-7316
1680-7324
9
11
2009
10.5194/acp-9-3709-2009
http://www.atmos-chem-phys.net/9/3709/2009/
http://www.atmos-chem-phys.net/9/3709/2009/acp-9-3709-2009.html
http://www.atmos-chem-phys.net/9/3709/2009/acp-9-3709-2009.pdf
3709
3720
2009-06-09
Real time chemical characterization of local and regional nitrate aerosols
M. Dall'Osto
R. M. Harrison
r.m.harrison@bham.ac.uk
H. Coe
P. I. Williams
J. D. Allan
National Centre for Atmospheric Science, Division of Environmental Health & Risk Management, School of Geography, Earth & Environmental Sciences, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
National Centre for Atmospheric Science, School of Earth, Atmospheric & Environmental Sciences, The University of Manchester, Simon Building Oxford Road, Manchester M13 9PL, UK
currently at: School of Physics & Centre for Climate & Air Pollution Studies, Environmental Change Institute National University of Ireland, Galway, Ireland
Nitrate aerosols make a very major contribution to PM<sub>2.5</sub> and PM<sub>10</sub>
in western Europe, but their sources and pathways have not been fully
elucidated. An Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) and a
Compact Time of Flight Aerosol Mass Spectrometer (C-ToF-AMS) were deployed
in an urban background location in London, UK, collecting data as part of
the REPARTEE-I experiment. During REPARTEE-I, daily PM<sub>10</sub> concentrations
ranged up to 43.6 μg m<sup>−3</sup>, with hourly nitrate concentrations
(measured by AMS) of up to 5.3 μg m<sup>−3</sup>. The application of the
ART-2a neural network algorithm to the ATOFMS data characterised the nitrate
particles as occurring in two distinct clusters (i.e. particle types). The
first (33.6% of particles by number) appeared to be locally produced in
urban locations during nighttime, whilst the second (22.8% of particles
by number) was regionally transported from continental Europe. Nitrate in
locally produced aerosol was present mainly in particles smaller than 300 nm, whilst the regional nitrate presented a coarser mode, peaking at 600 nm.
In both aerosol types, nitrate was found to be internally mixed with
sulphate, ammonium, elemental and organic carbon. Nitrate in regional
aerosol appeared to be more volatile than that locally formed. During
daytime, a core of the regionally transported nitrate aerosol particle type
composed of organic carbon and sulphate was detected.
Abdalmogith, S. S. and Harrison R. M..: An analysis of spatial and temporal properties of daily sulphate, nitrate and chloride concentrations at UK urban and rural sites, J. Environ. Monitor., 8, 691–699, 2006a.
Abdalmogith, S. S., Harrison, R. M., and Derwent, R. G.: Particulate sulphate and nitrate in southern England and Northern Ireland during 2002/3 and its formation in a photochemical trajectory model, Sci. Total. Environ., 368, 769–780, 2006b.
Abdalmogith, S. S. and Harrison, R. M.: The use of trajectory cluster analysis to examine the long-range transport of secondary inorganic aerosol in the UK, Atmos. Environ., 39, 6686–6695, 2005.
Adams, P. J., Seinfeld, J. H., Koch, D., Mickley, L., and Jacob, D.: General circulation model assessment of direct radiative forcing by the sulfate-nitrate-ammonium-water inorganic aerosol system, J. Geophys. Res.-Atmos., 106(D1), 1097–1111, 2001.
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. Environ., 38(34), 5745–5758, 2004.
Allan, J. D., Alfarra, M. R., Bower, K. N., Williams, P. I., Gallagher, M. W., Jimenez, J. L., McDonald, A. G., Nemitz, E., Canagaratna, M. R., Jayne, J. T., Coe, H., and Worsnop, D. R.: Quantitative sampling using an aerodyne aerosol mass spectrometer: 2. Measurements of fine particulate chemical composition in two UK cities (108, 4091, 2003), J. Geophys.Res.-Atmos., 108(D9), 4091, doi:10.1029/2002JD002359, 2003.
Allan, J. D., Coe, H., Bower, K. N., Alfarra, M. R., Delia, A. E., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch, T. B., Canagaratna, M. R., Jayne, J. T., and Worsnop, D. R.: Technical note: Extraction of chemically resolved mass spectra from aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922, 2004.
Allen, A. G., Harrison, R. M., and Erisman, J. W.: Field measurements of the dissociation of ammonium nitrate and ammonium chloride aerosols, Atmos. Environ., 23, 1591–1599, 1989
Bauer, S. E., Koch, D., Unger, N., Metzger, S. M., Shindell, D. T., and Streets, D. G.: Nitrate aerosols today and in 2030: a global simulation including aerosols and tropospheric ozone, Atmos. Chem. Phys., 7, 5043–5059, 2007.
Bouwman, A. F., Lee, D. S., Asman, W. A. H., Dentener, F. J., VanderHoek, K. W., and Olivier, J. G. J.: A global high-resolution emission inventory for ammonia, Global Biogeochem. Cy., 11(4), 561–587, 1997.
Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R. Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311(5757), 67–70, 2006.
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., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass Spectrom. Rev., 26(2), 185–222, 2007.
Carslaw, N., Carpenter, L., Plane, J. M. C., Allan, B., Burgess, R. A., Clemitshaw, K. C., Coe, H., and Penkett, S. A.: Simultaneous measurements of nitrate and peroxy radicals in the marine boundary layer, J. Geophys. Res., 102, (D15), 18917–18933, 1997.
Carson, P. G., Johnston, M. V., and Wexler, A. S.: Laser desorption/ionization of ultrafine aerosol particles, Rapid Commun. Mass Sp., 11(9), 993–996, 1997.
Charron, A., Harrison, R. M., and Quincey, P.: What are the sources and conditions responsible for exceedences of the 24 h PM$_10$ limit value (50 $\mu $g m-3) at a heavily trafficked London site?, Atmos. Environ., 41(9), 1960–1975, 2007.
Cozic, J., Verheggen, B., Mertes, S., Connolly, P., Bower, K., Petzold, A., Baltensperger, U., and Weingartner, E.: Scavenging of black carbon in mixed phase clouds at the high alpine site Jungfraujoch, Atmos. Chem. Phys., 7, 1797–1807, 2007.
Crane, R. I. and Evans, R. L.: Inertial deposition of particles in a bent pipe, J. Aerosol Sci., 8, 161–170, 1977.
Crosier, J., Allan, J. D., Coe, H., Bower, K. N., Formenti, P., and Williams, P. I.: Chemical composition of summertime aerosol in the Po Valley (Italy), northern Adriatic and Black Sea, Q. J. Roy. Meteor. Soc., 133, 61–75, 2007.
Cross, E. S., Slowik, J. G., Davidovits, P., Allan, J. D., Worsnop, D. R., Jayne, J. T., Lewis, D. K., Canagaratna, M., and Onasch, T. B.: Laboratory and ambient particle density determinations using light scattering in conjunction with aerosol mass spectrometry, Aerosol Sci. Technol., 41(4), 343–359, 2007.
Dall'Osto, M. and Harrison, R. M.: Chemical characterisation of single airborne particles in Athens (Greece) by ATOFMS, Atmos. Environ., 40, 7614–7631, 2006.
Dall'Osto, M., Harrison, R. M., Coe, H., and Williams, P.: Real-time secondary aerosol formation during a fog event in London, Atmos. Chem. Phys., 9, 2459–2469, 2009.
Draxler, R. R. and Rolph, G. D.: HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory) model access via NOAA ARL READY website (http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD.
Drewnick, F., Hings, S. S., DeCarlo, P., Jayne, J. T., Gonin, M., Fuhrer, K., Weimer, S., Jimenez, J. L., Demerjian, K. L., Borrmann, S., Worsnop, D. R.: A new Time-of-Flight Aerosol Mass Spectrometer (TOF-AMS) – instrument description and first field deployment, Aerosol Sci. Tech., 39, 637–658, 2005.
Hallquist, M., Stewart, D. J., Stephenson, S. K., and Cox, R. A.: Hydrolysis of N<sub>2</sub>O$_5$ on sub-micron sulfate aerosols, Phys. Chem. Chem. Phys., 5(16), 3453–3463, 2003.
Harrison, R. M., Jones, A. M. and Lawrence, R. G.: A pragmatic mass closure model for airborne particulate matter at urban background and roadside sites, Atmos. Environ., 37(35), 4927–4933, 2003.
Harrison, R. M., Jones, A. M., and Lawrence, R. G.: Major component composition of PM$_10$ and PM$_2.5$ from roadside and urban background sites, Atmos. Environ., 38(27), 4531–4538, 2004.
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(1–2), 49–70, 2000.
Liao, H., Chen, W. T., and Seinfeld, J. H.: Role of climate change in global predictions of future tropospheric ozone and aerosols, J. Geophys. Res.-Atmos., 111(D12), D1230, doi:10.1029/2005JD006852, 2006.
Liao, H., Seinfeld, J. H., Adams, P. J., and Mickley, L. J.: Global radiative forcing of coupled tropospheric ozone and aerosols in a unified general circulation model, J. Geophys. Res.-Atmos., 109(D16), D24204, doi:10.1029/2004JD005476, 2004.
Mansoori, B. A., Johnston, M. V., and Wexler, A. S.: Quantitation of ionic species in single microdroplets by online laser desorption/ionization, Anal. Chem., 66(21), 3681–3687, 1994.
Matthew, B. M., Middlebrook, A. M., and Onasch, T. B.: Collection efficiencies in an Aerodyne Aerosol Mass Spectrometer as a function of particle phase for laboratory generated aerosols, Aerosol Sci. Tech., 42(11), 884–898, 2008.
Mentel, T. F., Sohn, M., and Wahner, A.: Nitrate effect in the heterogeneous hydrolysis of dinitrogen pentoxide on aqueous aerosols, Phys. Chem. Chem. Phys., 1(24), 5451–5457, 1999.
Murphy, D. M.: The design of single particle laser mass spectrometers, Mass Spectrom. Rev., 26(2), 150–165, 2007.
Nemitz, E., Phillips G. J., Dall'Osto, M., Harrison, R. M., Williams, P. I., and Coe, H.: Concentrations and Fluxes of Inorganic Reactive Gases and Aerosols above London, Atmos. Chem. Phys. Discuss., in preparation, 2009.
Noble, C. A. and Prather, K. A.: Real-time single particle mass spectrometry: A historical review of a quarter century of the chemical analysis of aerosols, Mass Spectrom. Rev., 19(4), 248–274, 2000.
Qin, X. Y., Bhave, P. V., and Prather, K. A.: Comparison of two methods for obtaining quantitative mass concentrations from aerosol time-of-flight mass spectrometry measurements, Anal. Chem., 78(17), 6169–6178, 2006.
Petzold, A. and Schonlinner, K.: Multi-angle absorption photometry – a new method for the measurement of aerosol light absorption and atmospheric black carbon, Aerosol Sci., 35, 421–441, 2004.
Pui, D. Y. H., Romay-Novas, F., and Liu, B. Y. H.: Experimental study of particle deposition in bends of circular cross section, Aerosol Sci. Tech., 7, 301–15, 1987.
Rebotier, T. P. and Prather, K. A.: Aerosol time-of-flight mass spectrometry data analysis: A benchmark of clustering algorithms, Anal. Chim. Acta, 585(1), 38–54, 2007.
Reilly, P. T. A., Lazar, A. C., Gieray, R. A., Whitten, W. B., and Ramsey, J. M.: The elucidation of charge-transfer-induced matrix effects in environmental aerosols via real-time aerosol mass spectral analysis of individual airborne particles, Aerosol Sci. Tech., 33(1–2), 135–152, 2000
Schoolcraft, T. A., Constable, G. S., Jackson, B., Zhigilei, L. V., and Garrison, B. J.: Molecular dynamics simulations of laser disintegration of amorphous aerosol particles with spatially nonuniform absorption, Nucl. Instrum. Meth. A, 180, 245–250, 2001.
Silva, P. J. and Prather, K. A.: Interpretation of mass spectra from organic compounds in aerosol time-of-flight mass spectrometry, Anal. Chem., 72(15), 3553–3562, 2000.
Silva, P. J., Vawdrey, E. L., Corbett, M., and Erupe, M.: Fine particle concentrations and composition during wintertime inversions in Logan, Utah, USA, Atmos. Environ., 41(26), 5410–5422, 2007.
Song, X. H., Hopke, P. K., Fergenson, D. P., and Prather, K. A.: Classification of single particles analyzed by ATOFMS using an artificial neural network, ART-2A, Anal. Chem., 71(4), 860–865, 1999.
Spencer, M. T., Shields, L. G., Sodeman, D. A., Toner, S. M., and Prather, K A.: Comparison of oil and fuel particle chemical signatures with particle emissions from heavy and light duty vehicles, Atmos. Environ., 40(27), 5224–5235, 2006.
Suess, D. T. and Prather, K. A.: Mass spectrometry of aerosols, Chem. Rev., 99(10), 3007–3035, 1999.
Thomas, R. M.: Measurement of Speciated Aerosol Fluxes, PhD thesis, University of Manchester, 2007.
Thomson, D. S., Middlebrook, A. M., and Murphy, D. M.: Thresholds for laser-induced ion formation from aerosols in a vacuum using ultraviolet and vacuum-ultraviolet laser wavelengths, Aerosol Sci. Tech., 26(6), 544–559, 1997.
Williams, P. I., Gallagher, M. W., Choularton, T. W., Coe, H., Bower, K. N., and McFiggans, G.: Aerosol development and interaction in an urban plume, Aerosol Sci. Tech., 32(2), 120–126, 2000.
Yin, J. and Harrison, R. M.: Pragmatic mass closure study for PM$_1.0$, PM$_2.5$ and PM$_10$ at roadside, urban background and rural sites, Atmos. Environ., 42(5), 980, 2008.