Journal of Atmospheric Chemistry

, Volume 47, Issue 3, pp 223–241 | Cite as

Particle Size Distribution and Gas-Particle Partition of Polycyclic Aromatic Hydrocarbons in Helsinki Urban Area

  • Masahiko Shimmo
  • Karri Saarnio
  • Pasi Aalto
  • Kari Hartonen
  • Tuulia Hyötyläinen
  • Markku Kulmala
  • Marja-Liisa Riekkola


Ambient concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in Helsinki (Finland). Particle mass size distributions were obtained with a cascade impactor (12 stages) with glass fibre filters as substrates. Simultaneously with the impactor measurements, particulate and gaseous PAHs were collected on a quartz filter and XAD-2 adsorbent, respectively, for evaluation of gas-partition coefficients. Samples were analysed for PAHs by on-line coupled supercritical fluid extraction — liquid chromatography — gas chromatography — mass spectrometry. The impactor results showed that most of the PAHs in Helsinki urban area were concentrated in fine particles (<2.5 μm diameter) with unimode peak at about 1 μm. The results were comparable with the number distribution measured with a differential mobility particle sizer. Total amounts of PAHs (gas + particle) varied from 15 (acenaphthylene) to 1990 (fluorene) pg/m3. The PAHs lighter than 202 amu (pyrene and fluoranthene) were exclusively in gas phase, whereas those heavier than 202 amu were mostly associated with particles. A plot of the partition coefficients (logKp) versus the temperature dependent sub-cooled vapour pressures (logp L 0 ) showed a gradient of −0.66, which deviated from equilibrium state (gradient = −1).

polycyclic aromatic hydrocarbons cascade impactor size distribution supercritical fluid extraction liquid chromatography — gas chromatography 


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  1. Allen, J. O., Dookeran, N. M., Smith, K. A., Sarofim, A. F., Taghizadeh, K., and Lafleur, A. L., 1996: Measurement of polycyclic aromatic hydrocarbons associated with size-segregated atmospheric aerosols in Massachusetts, Environ. Sci. Technol. 30(3), 1023–1031.CrossRefGoogle Scholar
  2. Alves, C. A., Pio, C. A., and Duarte, A. C., 2000: Particulate size distributed organic compounds in a forest atmosphere, Environ. Sci. Technol. 34(20), 4287–4293.CrossRefGoogle Scholar
  3. Buehler, S. S., Basu, I., and Hites, R. A., 2001: A comparison of PAH, PCB, and pesticide concentrations in air at two rural site on Lake Superior, Environ. Sci. Tecchnol. 35(12), 2417–2422.Google Scholar
  4. Bøwadt, S. and Hawthorne, S. B., 1995: Supercritical fluid extraction in environmental analysis, J. Chromatogr. A 703(1+2), 549–571.Google Scholar
  5. Cecinato, A., Marino, F., Di Filippo, P., Lepore, L., and Possanzini, M., 1999: Distribution of nalkanes, polynuclear aromatic hydrocarbons and nitrated polynuclear aromatic hydrocarbons between the fine and coarse fractions of inhalable atmospheric particulates, J. Chromatogr. A 846(1+2), 255–264.Google Scholar
  6. Chester, T. L., Pinkiston, J. D., and Raynie, D. E., 1998: Supercritical fluid chromatography and extraction, Anal. Chem. 70(12), 301–319.CrossRefGoogle Scholar
  7. Dachs, J. D. and Eisenreich, S. J., 2000: Adsorption onto aerosol soot carbon dominates gas-particle partitioning of polycyclic aromatic hydrocarbons, Environ. Sci. Technol. 34(17), 3690–3697.CrossRefGoogle Scholar
  8. Didyk, B. M., Simoneit, B. R. T., Pezoa, L. A., Riveros, M. L., and Flores, A. A., 2000: Urban aerosol particle of Santiago, Chile: organic contents and molecular characterization, Atmos. Environ. 34(8), 1167–1179.CrossRefGoogle Scholar
  9. European Commission, 2001: Ambient air pollution by polycyclic aromatic hydrocarbons (PAH), Position Paper, Luxembourg.Google Scholar
  10. Fernández, P., Grimalt, J. O., and Vilanova, R. M., 2002: Atmospheric gas-particle partitioning of polycyclic aromatic hydrocarbons in high mountain regions of Europe, Environ. Sci. Technol. 36(6), 1162–1168.Google Scholar
  11. Finlayson-Pitts, B. J. and Pitts, J. N. Jr., 1999: Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications, Academic Press, California, pp. 21–23.Google Scholar
  12. Garivait, H., Polprasert, C., Yoshizumi, K., and Reutergardh, L. B., 1999: Airborne polycyclic aromatic hydrocarbons (PAH) in Bangkok urban air I. Characterization and quantification, Polycyclic Aromat. Compd. 13, 313–327.Google Scholar
  13. Garivait, H., Polprasert, C., Yoshizumi, K., and Reutergardh, L. B., 2001: Airborne polycyclic aromatic hydrocarbons (PAH) in Bangkok urban air II. Level and distribution, Polycyclic Aromat. Compd. 18, 325–350.Google Scholar
  14. Gigliotti, C. L., Dachs, J., Nelson, E. D., Brunciak, P. A., and Eisenreich, S. J., 2000: Polycyclic aromatic hydrocarbons in the New Jersey coastal atmosphere, Environ. Sci. Technol. 34(17), 3547–3554.CrossRefGoogle Scholar
  15. Goss, K-W. and Schwarzenbach, R. P., 1998: Gas/solid and gas/liquid partitioning of organic components: Critical evaluation of the interpretation of equilibrium constants, Environ. Sci. Technol. 32(14), 2025–2032.CrossRefGoogle Scholar
  16. Harrison, R. M., Smith, D. J. T., and Luhana, L., 1996: Source appointment of atmospheric polycyclic aromatic hydrocarbons collected from an urban location in Birmingham, U.K., Environ. Sci. Technol. 30(3), 825–832.CrossRefGoogle Scholar
  17. Hartonen, K., Bøwadt, S., Hawthorne, S., and Riekkola, M.-L., 1997: Supercritical fluid extraction with solid-phase trapping of chlorinated and brominated pollutants from sediment samples, J. Chromatogr. A 774, 229–242.CrossRefGoogle Scholar
  18. Hillamo, R. E. and Kauppinen, E. I., 1991: On the performance of the Berner low pressure impactor, Aerosol Sci. Technol. 14(1), 33–47.Google Scholar
  19. Hinds, W. C., 1982: Aerosol Technology, Wiley, New York, p. 122.Google Scholar
  20. Hyötyläinen, T. and Riekkola, M.-L., 2001: Potential of on-line coupled liquid chromatography-gas chromatography in the analysis of complex samples, Recent Res. Devel. Anal. Chem. 1, 21–43.Google Scholar
  21. Kaupp, H. and McLachlan, M.S., 1999: Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polucyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition, Atmos. Environ. 33(1), 85–95.Google Scholar
  22. Kaupp, H. and McLachlan, M. S., 2000: Distribution of polychlorinated dibenzo-P-dioxins and fibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) within the full size range of atmospheric particles, Atmos. Environ. 34(1) 73–83.CrossRefGoogle Scholar
  23. Kirchstetter, T. W., Corrigan, C. E., and Novakov, T., 2001: Laboratory and field investigation of the adsorption of gaseous organic compounds onto quartz filters, Atmos. Environ. 35(9), 1663–1671.CrossRefGoogle Scholar
  24. Kiss, G., Puchony-Varga, Z., Tolnai, B., Varga, B., Gelencśer, A., Krivácsy, Z., and Hlavay, J., 2001: The seasonal changes in the concentration of polycyclic aromatic hydrocarbons in precipitation and arosol near Lake Balaton, Hungary, Environ. Pollut. 114, 55–61.CrossRefGoogle Scholar
  25. Lim, L. H., Harrison, R. M., and Harrad, S., 1999: The concentration of traffic to atmospheric concentrations of polycyclic aromatic hydrocarbons, Environ. Sci. Technol. 33(20), 3538–3542.CrossRefGoogle Scholar
  26. Lohmann, R., Harner, T., Thomas, G. O., and Jones, K. C., 2000: A comparative study of the gas-particle partitioning of PCDD/Fs, PCBs, and PAHs, Environ. Sci. Technol. 34(23), 4943–4951.CrossRefGoogle Scholar
  27. Mader, B. T. and Pankow, J. F., 2000: Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 1. Partitioning of polychlorinated dibenzodioxins, polychlorinated dibenzofurans and polycyclic aromatic hydrocarbons to Teflon membrane filters, Atmos. Environ. 34(28), 4879–4887.CrossRefGoogle Scholar
  28. Mader, B. T. and Pankow, J.F., 2001a: Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 2. Partitioning of polychlorinated dibenzodioxins, polychlorinated dibenzofurans, and polycyclic aromatic hydrocarbons to quartz fiber filters, Atmos. Environ. 35(7), 1217–1223.CrossRefGoogle Scholar
  29. Mader, B. T. and Pankow, J. F., 2001b: Gas/solid partitioning of semivolatile organic compounds (SOCs) to air filters. 3. An analysis of gas adsorption artifacts in measurements of atmospheric SOCs and organic carbon (OC). When using teflon membrane filters and quartz fiber filters, Environ. Sci. Technol. 35(17), 3422–3432.CrossRefGoogle Scholar
  30. Mészáros, E., Barcza, T., Gelencsér, A., Hlavay, J., Kiss, G., Krivácsy, Z., Molnár, A., and Polyák, K., 1997: Size distributions of inorganic and organic species in the atmospheric aerosol in Hungary, J. Aerosol Sci. 28(7), 1163–1175.Google Scholar
  31. Mondello, L., Dugo, P., Dugo, G., Lewis, A. C., and Bartle, K. D., 1999: High-performance liquid chromatography coupled on-line with high resolution gas chromatography. State of the art, J. Chromatogr. A. 842(1+2), 373–390.Google Scholar
  32. Offenberg, J. H. and Baker, J. E., 1999: Aerosol size distributions of polycyclic aromatic hydrocarbons in urban and over-water atmosphere, Environ. Sci. Technol. 33(19), 3324–3331.CrossRefGoogle Scholar
  33. Offenberg, J. H. and Baker, J. E., 2000: The influence of aerosol size and organic carbon content on gas/particle partitioning of polycyclic aromatic hydrocarbons (PAHs), Atmos. Environ. 36(7), 1205–1220.Google Scholar
  34. Peters, A. J., Lane, D. A., Gundel, L. A., Northcott, G. L., and Jones, K. C., 2000: A comparison of high volume and diffusion denuder samplers for measuring demivolatile organic compounds in the atmosphere, Environ. Sci. Technol. 34(23), 5001–5006.CrossRefGoogle Scholar
  35. Pio, C., Aves, C., and Duarte, A., 2001: Organic components of aerosols in a forested area of central Greece, Atmos. Environ. 35(2), 389–401.CrossRefGoogle Scholar
  36. Sanusi, A., Millet, M., Mirabel, P., and Wortham, H., 1999: Gas-particle partitioning of pesticides in atmospheric samples, Atmos. Environ. 33(29), 4941–4951.CrossRefGoogle Scholar
  37. Seinfeld, J. H. and Pandis, S. N., 1998: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, Wiley, New York, p. 426.Google Scholar
  38. Sheu, H.-L., Lee, W.-J., Lin, S. J., Fang, G.-C., Chang, H.-C., and You, W.-C., 1997: Particle-bound PAH contents in ambient air, Environ. Pollut. 96(3), 369–382.CrossRefGoogle Scholar
  39. Shimmo, M., Hyötyläinen, T., Hartonen, K., and Riekkola, M.-L., 2001: On-line coupled supercritical fluid extraction-liquid chromatography-gas chromatography-mass spectrometry for the analysis of organic acids, J. Microcol. Sep. 13(5), 202–210.CrossRefGoogle Scholar
  40. Shimmo, M., Adler, H., Hyötyläinen, T., Hartonen, K., Kulmala, M., and Riekkola, M.-L., 2002: Analysis of particulate polycyclic aromatic hydrocarbons by on-line coupled supercritical fluid extraction-liquid chromatography-gas chromatography-mass spectrometry, Atmos. Environ. 36(18), 2985–2995.CrossRefGoogle Scholar
  41. Simcik, M. F., Franz, T.P., Zhang, H., and Eisenreich, S. J., 1998: Gas-particle partitioning of PCBs and PAHs in the Chicago urban and adjacent coastal atmosphere: States of equilibrium, Environ. Sci. Technol. 32(2), 251–257.CrossRefGoogle Scholar
  42. Sugiyama, T., Amagai, T., Matsushita, H., and Soma, M., 1999: Size distribution of indoor airborne particulates collected by a low, Indoor Built. Environ. 8, 361–369.CrossRefGoogle Scholar
  43. Tsai, P.-J., Shieh, H.-Y., Lee, W.-J., and Lai, S.-O., 2001: Health-risk assessment for workers exposed to polycyclic aromatic hydrocarbons (PAHs) in a carbon black manufacturing industry, Sci. Total. Environ. 278, 137–150.CrossRefGoogle Scholar
  44. Turpin, B. J., Saxena, P., and Andrews, E., 2000: Measuring and simulating particulate organics in the atmosphere: problems and prospects, Atmos. Environ 34(18), 2983–3013.CrossRefGoogle Scholar
  45. U.S. Environment Protection Agency, 1986: Modified method 5 sample train, Method 0010.Google Scholar
  46. U.S. Environment Protection Agency, 1997: Determination of polycyclic aromatic hydrocarbons in ambient air using gas chromatography/mass spectrometry, Compendium method TO-13A.Google Scholar
  47. Venkataraman, C., Thomas, S., and Kulkarni, P., 1999: Size distribution of polycyclic aromatic hydrocarbons — gas/particle partitioning to urban aerosols J. Aerosol Sci. 30(6), 759–770.Google Scholar
  48. World Health Organization, 2000: Air Quality Guidelines for Europe, WHO European Series, WHO Regional Bureau, Copenhagen.Google Scholar
  49. Yamasaki, H., Kuwata, K., and Kuge, Y., 1984, Determination of vapor pressure of polycyclic aromatic hyderocarbons in the supercooled liquid phase and their adsorption on airborne particulate matter, Nippon Kagaku Kaishi 8, 1324–1329.Google Scholar

Copyright information

© Kluwer Academic Publishers 2004

Authors and Affiliations

  • Masahiko Shimmo
    • 1
  • Karri Saarnio
    • 1
  • Pasi Aalto
    • 2
  • Kari Hartonen
    • 1
  • Tuulia Hyötyläinen
    • 1
  • Markku Kulmala
    • 2
  • Marja-Liisa Riekkola
    • 1
  1. 1.Laboratory of Analytical Chemistry, Department of ChemistryUniversity of HelsinkiFinland
  2. 2.Division of Atmospheric Sciences, Department of Physical SciencesUniversity of HelsinkiFinland

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