Analytical and Bioanalytical Chemistry

, Volume 396, Issue 3, pp 1321–1330

Determination of 43 polycyclic aromatic hydrocarbons in air particulate matter by use of direct elution and isotope dilution gas chromatography/mass spectrometry

  • Zheng Li
  • Erin N. Pittman
  • Debra A. Trinidad
  • Lovisa C. Romanoff
  • James Mulholland
  • Andreas Sjödin
Original Paper

Abstract

We are reporting a method for measuring 43 polycyclic aromatic hydrocarbons (PAH) and their methylated derivatives (Me-PAHs) in air particulate matter (PM) samples using isotope dilution gas chromatography/high-resolution mass spectrometry (GC/HRMS). In this method, PM samples were spiked with internal standards, loaded into solid phase extraction cartridges, and eluted by dichloromethane. The extracts were concentrated, spiked with a recovery standard, and analyzed by GC/HRMS at 10,000 resolution. Sixteen 13C-labeled PAHs and two deuterated Me-PAHs were used as internal standards to account for instrument variability and losses during sample preparation. Recovery of labeled internal standards was in the range of 86–115%. The proposed method is less time-consuming than commonly used extraction methods, such as sonication and accelerated solvent extraction (ASE), and it eliminates the need for a filtration step required after the sonication extraction method. Limits of detection ranged from 41 to 332 pg/sample for the 43 analytes. This method was used to analyze reference materials from the National Institute of Standards and Technology. The results were consistent with those from ASE and sonication extraction, and these results were also in good agreement with the certified or reference concentrations. The proposed method was then used to measure PAHs on PM2.5 samples collected at three sites (urban, suburban, and rural) in Atlanta, GA. The results showed distinct seasonal and spatial variation and were consistent with an earlier study measuring PM2.5 samples using an ASE method, further demonstrating the compatibility of this method and the commonly used ASE method.

Figure

A schematic illustration of the direct elution set up

Keywords

Polycyclic aromatic hydrocarbon PAH PM Method GC/MS 

Abbreviations

PM

Particulate matter

PM2.5

Particulate matter with aerodynamic diameters less than 2.5 μm

PAH

Polycyclic aromatic hydrocarbon

ASE

Accelerated solvent extraction

GC/MS

Gas chromatography/mass spectrometry

GC/HRMS

Gas chromatography/high-resolution mass spectrometry

References

  1. 1.
    Ostro B, Feng WY, Broadwin R, Green S, Lipsett M (2007) Environ Health Perspect 115:13–19CrossRefGoogle Scholar
  2. 2.
    Pope CA III, Burnett RT, Thurston GD, Thun MJ, Calle EE, Krewski D, Godleski JJ (2004) Circulation 109:71–77CrossRefGoogle Scholar
  3. 3.
    ATSDR (1995) Toxicological profile for polycyclic aromatic hydrocarbons. Agency for Toxic Substances and Disease Registry, Atlanta http://www.atsdr.cdc.gov/toxprofiles/tp69.html Accessed 14 August 2009Google Scholar
  4. 4.
    IARC (1983) IARC monographs on the evaluation of carcinogenic risk of chemicals to man: polycyclic aromatic compounds. http://monographs.iarc.fr/ENG/Monographs/vol32/volume32.pdf Accessed 14 August 2009.
  5. 5.
    Bostrom CE, Gerde P, Hanberg A, Jernstrom B, Johansson C, Kyrklund T, Rannug A, Tornqvist M, Victorin K, Westerholm R (2002) Environ Health Perspect 110(Suppl 3):451–488Google Scholar
  6. 6.
    Ramesh A, Walker SA, Hood DB, Guillen MD, Schneider K, Weyand EH (2004) Int J Toxicol 23:301–333CrossRefGoogle Scholar
  7. 7.
    U.S.EPA (1990) Clean air act, sec 112: Hazardous air pollutantsGoogle Scholar
  8. 8.
    Eiguren-Fernandez A, Miguel AH, Froines JR, Thurairatnam S, Avol EL (2004) Aerosol Sci Tech 38:447–455CrossRefGoogle Scholar
  9. 9.
    Re-Poppi N, Santiago-Silva M (2005) Atmos Environ 39:2839–2850CrossRefGoogle Scholar
  10. 10.
    Cancio JAL, Castellano AV, Martin SS, Rodriguez JFS (2004) Water Air Soil Pollut 154:127–138CrossRefGoogle Scholar
  11. 11.
    Duan JC, Bi XH, Tan JH, Sheng GY, Fu JM (2005) Atmos Res 78:190–203CrossRefGoogle Scholar
  12. 12.
    Ohura T, Amagai T, Sugiyama T, Fusaya M, Matsushita H (2004) Atmos Environ 38:2045–2054CrossRefGoogle Scholar
  13. 13.
    Bourotte C, Forti MC, Taniguchi S, Bicego MC, Lotufo PA (2005) Atmos Environ 39:3799–3811CrossRefGoogle Scholar
  14. 14.
    Sanderson EG, Raqbi A, Vyskocil A, Farant JP (2004) Atmos Environ 38:3417–3429CrossRefGoogle Scholar
  15. 15.
    Simo R, Grimalt JO, Albaiges J (1997) Environ Sci Technol 31:2697–2700CrossRefGoogle Scholar
  16. 16.
    Yunker MB, Macdonald RW, Vingarzan R, Mitchell RH, Goyette D, Sylvestre S (2002) Org Geochem 33:489–515CrossRefGoogle Scholar
  17. 17.
    Zakaria MP, Takada H, Tsutsumi S, Ohno K, Yamada J, Kouno E, Kumata H (2002) Environ Sci Technol 36:1907–1918CrossRefGoogle Scholar
  18. 18.
    Vondracek J, Svihalkova-Sindlerova L, Pencikova K, Marvanova S, Krcmar P, Ciganek M, Neca J, Trosko JE, Upham B, Kozubik A, Machala M (2007) Environ Toxicol Chem 26:2308–2316CrossRefGoogle Scholar
  19. 19.
    Ramdahl T (1983) Nature 306:580–583CrossRefGoogle Scholar
  20. 20.
    McDonald JD, Zielinska B, Fujita EM, Sagebiel JC, Chow JC, Watson JG (2000) Environ Sci Technol 34:2080–2091CrossRefGoogle Scholar
  21. 21.
    Villalobos-Pietrini R, Amador-Munoz O, Waliszewski S, Hernandez-Mena L, Munive-Colin Z, Gomez-Arroyo S, Bravo-Cabrera JL, Frias-Villegas A (2006) Atmos Environ 40:5845–5857CrossRefGoogle Scholar
  22. 22.
    Li Z, Sjodin A, Porter EN, Patterson DG Jr, Needham LL, Lee S, Russell AG, Mulholland JA (2009) Atmos Environ 43:1043–1050CrossRefGoogle Scholar
  23. 23.
    Lima ALC, Eglinton TI, Reddy CM (2003) Environ Sci Technol 37:53–61CrossRefGoogle Scholar
  24. 24.
    Li Z, Porter EN, Sjodin A, Needham LL, Lee S, Russell AG, Mulholland JA (2009) Atmos Environ 43:4187–4193CrossRefGoogle Scholar
  25. 25.
    U.S.EPA. Determination of Polycyclic Aromatic Hydrocarbons (PAHs) In ambient air using Gas Chromatography/Mass Spectrometry (GC/MS). 1-11-1999. http://www.epa.gov/ttn/amtic/files/ambient/airtox/to-13arr.pdf Accessed 14 August 2009
  26. 26.
    Christensen A, Ostman C, Westerholm R (2005) Analytical and Bioanalytical Chemistry 381:1206–1216CrossRefGoogle Scholar
  27. 27.
    U.S.EPA. Analysis of PCBs, pesticides, and PAHs in air and precipitation samples: sample preparation procedures. 3-1-1995. http://www.epa.gov/glnpo/lmmb/methods/samprep2.pdf Accessed 14 August 2009.
  28. 28.
    Pino V, Ayala JH, Afonso AM, Gonzalez V (2000) J Chromatogr A 869:515–522CrossRefGoogle Scholar
  29. 29.
    Pleil JD, Vette AF, Rappaport SM (2004) J Chromatogr A 1033:9–17CrossRefGoogle Scholar
  30. 30.
    Chester TL, Pinkston JD, Raynie DE (1998) Anal Chem 70:301R–319RCrossRefGoogle Scholar
  31. 31.
    Lintelmann J, Fischer K, Karg E, Schroppel A (2005) Analytical and Bioanalytical Chemistry 381:508–519CrossRefGoogle Scholar
  32. 32.
    Burkhardt MR, Zaugg SD, Burbank TL, Olson MC, Iverson JL (2005) Anal Chim Acta 549:104–116CrossRefGoogle Scholar
  33. 33.
    Olivella MA (2005) Analytical and Bioanalytical Chemistry 383:107–114CrossRefGoogle Scholar
  34. 34.
    Berset JD, Holzer R (1999) J Chromatogr A 852:545–558CrossRefGoogle Scholar
  35. 35.
    Hollender J, Koch B, Lutermann C, Dott W (2003) Int J Environ Anal Chem 83:21–32CrossRefGoogle Scholar
  36. 36.
    Butler AJ, Andrew MS, Russell AG (2003) J Geophys Res 108:8415–8425CrossRefGoogle Scholar
  37. 37.
    Bence AE, Kvenvolden KA, Kennicutt MC (1996) Org Geochem 24:7–42CrossRefGoogle Scholar
  38. 38.
    Boden AR, Reiner EJ (2004) Polycycl Aromat Compd 24:309–323CrossRefGoogle Scholar
  39. 39.
    Ravindra K, Bencs L, Wauters E, de Hoog J, Deutsch F, Roekens E, Bleux N, Berghmans P, Van Grieken R (2006) Atmos Environ 40:771–785CrossRefGoogle Scholar
  40. 40.
    Prycek J, Ciganek M, Simek Z (2006) Int J Environ Anal Chem 86:313–324CrossRefGoogle Scholar
  41. 41.
    Bergvall C, Westerholm R (2008) Analytical and Bioanalytical Chemistry 391:2235–2248CrossRefGoogle Scholar
  42. 42.
    NIST (2005) NISTIR 7303: Intercomparison program for organic speciation in PM2.5 air particulate matter: description and results for trial IIIGoogle Scholar
  43. 43.
    NIST (2009) Standard reference material 1649b: certificate of analysis. https://www-s.nist.gov/srmors/certificates/1649b.pdf Accessed 14 August 2009
  44. 44.
    Ludykar D, Westerholm R, Almen J (1999) Sci Total Environ 235:65–69CrossRefGoogle Scholar
  45. 45.
    Tsapakis M, Stephanou EG (2005) Environ Pollut 133:147–156CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  • Zheng Li
    • 1
  • Erin N. Pittman
    • 1
  • Debra A. Trinidad
    • 1
  • Lovisa C. Romanoff
    • 1
  • James Mulholland
    • 2
  • Andreas Sjödin
    • 1
  1. 1.Centers for Disease Control and PreventionAtlantaUSA
  2. 2.School of Environmental and Civil EngineeringGeorgia Institute of TechnologyAtlantaUSA

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