Analytical and Bioanalytical Chemistry

, Volume 407, Issue 12, pp 3509–3516 | Cite as

Behavior of PAH/mineral associations during thermodesorption: impact for the determination of mineral retention properties towards PAHs

  • Coralie BiacheEmail author
  • Catherine Lorgeoux
  • Alain Saada
  • Pierre Faure
Research Paper


Polycyclic aromatic hydrocarbons (PAHs) associated with two minerals (silica sand and bentonite) presenting opposite retention properties were analyzed with a thermodesorption (Td)-GC-MS coupling in order to validate this technique as a new and rapid way to evaluate the solid sorption properties. Two analysis modes were used, evolved gas analysis (EGA) and Td with cryo-trap. EGA allowed a real-time monitoring of the compounds desorbed during a temperature program and gave a first screening of the samples while Td gave more precise indications on compound abundances for selected temperature ranges. When associated with silica sand, PAHs were released at relatively low temperatures (<300 °C) close to corresponding boiling point, whereas for the PAH/bentonite mixture, PAHs were desorbed at much higher temperatures; they were also present in much lower abundance and were associated with mono-aromatic compounds. With bentonite, the PAH abundances decreased and the mono-aromatics increased with the increasing PAH molecular weight. These results indicated a clear PAH retention by the bentonite due to polymerization, followed by a thermal cracking at higher temperatures. The Td-GC-MS was proven to efficiently underline differences in retention properties of two minerals, and this study highlights the great potential of this technique to evaluate compound/matrix bond strength and interaction.


Evolved gas analysis Thermal desorption Bentonite Silica sand Polycyclic aromatic hydrocarbon Sorption 



This study was funded by the Lorraine Energy and Environment Carnot Institute (ICEEL) and the French Geological Survey (BRGM). We thank the GISFI (French Scientific Interest Group–Industrial Wasteland, We are also grateful to Angelina Razafitianamaharavo for the soil-specific area determination, and we thank Dr. Manuel Pelletier and Dr. Fabien Thomas for the helpful discussions. We also thank Axel Bart from SRA for technical support.

Supplementary material

216_2015_8547_MOESM1_ESM.pdf (54 kb)
ESM 1 (PDF 54 kb)


  1. 1.
    Keith LH, Telliard WA (1979) Priority pollutants I—a perspective view. Environ Sci Technol 13:416–423CrossRefGoogle Scholar
  2. 2.
    Cerniglia CE (1992) Biodegradation of polycyclic aromatic hydrocarbons. Biodegradation 3:351–368CrossRefGoogle Scholar
  3. 3.
    Lahlou M, Ortega-Calvo JJ (1999) Bioavailability of labile and desorption-resistant phenanthrene sorbed to montmorillonite clay containing humic fractions. Environ Toxicol Chem 18:2729–2735CrossRefGoogle Scholar
  4. 4.
    Hwang S, Cutright TJ (2002) Impact of clay minerals and DOM on the competitive sorption/desorption of PAHs. Soil Sediment Contam 11:269–291CrossRefGoogle Scholar
  5. 5.
    Karimi-Lotfabad S, Pickard MA, Gray MR (1996) Reactions of polynuclear aromatic hydrocarbons on soil. Environ Sci Technol 30:1145–1151CrossRefGoogle Scholar
  6. 6.
    Badea S-L, Lundstedt S, Liljelind P, Tysklind M (2013) The influence of soil composition on the leachability of selected hydrophobic organic compounds (HOCs) from soils using a batch leaching test. J Hazard Mater 254–255:26–35CrossRefGoogle Scholar
  7. 7.
    Biache C, Kouadio O, Lorgeoux C, Faure P (2014) Impact of clay mineral on air oxidation of PAH-contaminated soils. Environ Sci Pollut Res: 11017–11026Google Scholar
  8. 8.
    Ghislain T, Faure P, Biache C, Michels R (2010) Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils. Environ Sci Technol 44:8547–8552CrossRefGoogle Scholar
  9. 9.
    Roy WR, Krapac IG, Chou SFJ, Griffin RA (1991) Batch-type procedures for estimating soil adsorption of chemicals. EPA/530-SW-87-006-FGoogle Scholar
  10. 10.
    Gaboriau H, Saada A (2001) Influence of heavy organic pollutants of anthropic origin on PAH retention by kaolinite. Chemosphere 44:1633–1639CrossRefGoogle Scholar
  11. 11.
    Lafargue E, Marquis F, Pillot D (1998) Rock-Eval 6 applications in hydrocarbon exploration, production, and soil contaminations studies. Rev Inst Fr Pétrol 53:421–437Google Scholar
  12. 12.
    Cuypers C, Grotenhuis T, Nierop KGJ, Franco EM, de Jager A, Rulkens W (2002) Amorphous and condensed organic matter domains: the effect of persulfate oxidation on the composition of soil/sediment organic matter. Chemosphere 48:919–931CrossRefGoogle Scholar
  13. 13.
    Siewert C (2001) Investigation of the thermal and biological stability of soil organic matter. Shaker, AachenGoogle Scholar
  14. 14.
    Popp P, Bauer C, Hauser B, Keil P, Wennrich L (2003) Extraction of polycyclic aromatic hydrocarbons and organochlorine compounds from water: a comparison between solid-phase microextraction and stir bar sorptive extraction. J Sep Sci 26:961–967CrossRefGoogle Scholar
  15. 15.
    Popp P, Keil P, Montero L, Rückert M (2005) Optimized method for the determination of 25 polychlorinated biphenyls in water samples using stir bar sorptive extraction followed by thermodesorption-gas chromatography/mass spectrometry. J Chromatogr A 1071:155–162CrossRefGoogle Scholar
  16. 16.
    Beiner K, Plewka A, Haferkorn S, Iinuma Y, Engewald W, Herrmann H (2009) Quantification of organic acids in particulate matter by coupling of thermally assisted hydrolysis and methylation with thermodesorption-gas chromatography–mass spectrometry. J Chromatogr A 1216:6642–6650CrossRefGoogle Scholar
  17. 17.
    Haunold A, Rosenberg E, Grasserbauer M (1997) An improved sampling strategy for the measurement of VOCs in air, based on cooled sampling and analysis by thermodesorption-GC-MS/FID. Int J Environ Anal Chem 67:157–172CrossRefGoogle Scholar
  18. 18.
    Zhao J, Pa P, Song J, Ma S, Sheng G, Fu J (2009) Characterization of organic matter in total suspended particles by thermodesorption and pyrolysis-gas chromatography-mass spectrometry. J Environ Sci 21:1658–1666CrossRefGoogle Scholar
  19. 19.
    Faure P, Landais P (2001) Rapid contamination screening of river sediments by flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS) and thermodesorption GC–MS (TdGC–MS). J Anal Appl Pyrolysis 57:187–202CrossRefGoogle Scholar
  20. 20.
    Faure P, Vilmin F, Michels R, Jarde E, Mansuy L, Elie M, Landais P (2002) Application of thermodesorption and pyrolysis-GC–AED to the analysis of river sediments and sewage sludges for environmental purpose. J Anal Appl Pyrolysis 62:297–318CrossRefGoogle Scholar
  21. 21.
    Terán A, Gonzalez-Vila FJ, Gonzalez-Perez JA (2009) Detection of organic contamination in sediments by double-shoot pyrolysis–GC/MS. Environ Chem Lett 7:301–308CrossRefGoogle Scholar
  22. 22.
    Lide DR (ed) (2004) Handbook of chemistry and physics. 84th edn. CRC PressGoogle Scholar
  23. 23.
    Wold Health Organisation (2014) International programme on chemical safety. Accessed 30 Oct 2014
  24. 24.
    U.S. National Library of Medicine (2014) TOXNET Toxicology Data Network. Accessed 30 Oct 2014
  25. 25.
    National Institute of Standards and Technology (2014) Chemistry WebBook. Accessed 30 Oct 2014
  26. 26.
    Faure P, Jeanneau L, Lannuzel F (2006) Analysis of organic matter by flash pyrolysis-gas chromatography–mass spectrometry in the presence of Na-smectite: when clay minerals lead to identical molecular signature. Org Geochem 37:1900–1912CrossRefGoogle Scholar
  27. 27.
    Faure P, Schlepp L, Mansuy-Huault L, Elie M, Jardé E, Pelletier M (2006) Aromatization of organic matter induced by the presence of clays during flash pyrolysis-gas chromatography–mass spectrometry (PyGC–MS): a major analytical artifact. J Anal Appl Pyrolysis 75:1–10CrossRefGoogle Scholar
  28. 28.
    Kopinke F-D, Remmler M (1995) Reactions of hydrocarbons during thermodesorption from sediments. Thermochim Acta 263:123–139CrossRefGoogle Scholar
  29. 29.
    Espitalié J, Senga Makadi K, Trichet J (1984) Role of the mineral matrix during kerogen pyrolysis. Org Geochem 6:365–382CrossRefGoogle Scholar
  30. 30.
    Saxby JD, Chatfield P, Taylor GH, Fitzgerald JD, Kaplan IR, Lu ST (1992) Effect of clay minerals on products from coal maturation. Org Geochem 18:373–383CrossRefGoogle Scholar
  31. 31.
    Fagbemi L, Khezami L, Capart R (2001) Pyrolysis products from different biomasses: application to the thermal cracking of tar. Appl Energy 69:293–306CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Coralie Biache
    • 1
    • 2
    Email author
  • Catherine Lorgeoux
    • 3
    • 4
  • Alain Saada
    • 5
  • Pierre Faure
    • 1
    • 2
  1. 1.Université de Lorraine, LIEC, UMR7360Vandœuvre-lès-NancyFrance
  2. 2.CNRS, LIEC, UMR7360Vandœuvre-lès-NancyFrance
  3. 3.Université de Lorraine, GeoRessources, UMR7359Vandœuvre-lès-NancyFrance
  4. 4.CNRS, GeoRessources, UMR7359Vandœuvre-lès-NancyFrance
  5. 5.BRGMOrléans Cedex 2France

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