Applied Physics B

, 125:6 | Cite as

Measurement and extrapolation modeling of PAH laser-induced fluorescence spectra at elevated temperatures

  • Yiran Zhang
  • Lijun Wang
  • Peng Liu
  • Youping Li
  • Reggie Zhan
  • Zhen Huang
  • He LinEmail author


The laser-induced fluorescence technique is widely used in the measurement of polycyclic aromatic hydrocarbons (PAHs) in sooting flames. One of the main limitations is the absence of the PAH fluorescence spectra at elevated temperatures. In this study, fluorescence spectra and photophysical properties of five typical PAHs were experimentally studied in the temperature range of 673–1373 K in an optical cell. The experimental results indicated that the fluorescence spectra of PAHs were greatly sensitive to PAH structures and were likely to shift to the red and became broader as temperature increases. Further, we also observed that absorption cross sections of PAHs increased linearly as a function of temperature. Fluorescence quantum yields, which were calculated using integral fluorescence intensities and absorption cross sections, decreased monotonically with increasing temperature. However, the descent gradients of different PAHs were quite different, e.g., naphthalene, fluoranthene and fluorene were more sensitive to temperature, and their fluorescence production was much lower at elevated temperature compared with phenanthrene and pyrene. In order to investigate the fluorescence quantum yields at higher temperatures (up to 2000 K), which cannot be measured in the optical cell, a multistep decay model was established and optimized based on experimental results. At temperatures between 1373 and 2000 K, the extrapolation results indicated that fluorescence quantum yields of phenanthrene and pyrene would be two orders of magnitude higher than those of naphthalene, fluorene and fluoranthene. This contributed to explaining that the PAH fluorescence signals emitted from phenanthrene and pyrene were stronger than those emitted from naphthalene in flames, although the concentrations of phenanthrene and pyrene were much lower than that of naphthalene in flames.



This work was supported by the National Natural Science Foundation of China (91441129, 51210010) and the National Key R&D Program of China (2016YFC0208000).

Supplementary material

340_2018_7115_MOESM1_ESM.docx (841 kb)
Supplementary material 1 (DOCX 840 KB)


  1. 1.
    C.L. Friedman, Y. Zhang, N.E. Selin, Climate change and emissions impacts on atmospheric PAH transport to the Arctic. Environ. Sci. Technol. 48, 429–437 (2014)ADSCrossRefGoogle Scholar
  2. 2.
    B. Maliszewska-Kordybach, Sources, concentrations, fate and effects of polycyclic aromatic hydrocarbons (PAHs) in the environment. Part A: PAHs in air. Pol. J. Environ. Stud. 8, 131–136 (1999)Google Scholar
  3. 3.
    S. Mayoralasalises, S. Diazlobato, Air pollution and lung cancer. Curr. Respir. Med. Rev. 8, 982–983 (2012)Google Scholar
  4. 4.
    M.M. Mumtaz, J.D. George, K.W. Gold, W. Cibulas, C.T. Derosa, ATSDR evaluation of health effects of chemicals. IV. Polycyclic aromatic hydrocarbons (PAHs): understanding a complex problem. Toxicol. Ind. Health 12, 742 (1996)CrossRefGoogle Scholar
  5. 5.
    F.P. Perera, Environment and cancer: who are susceptible? Science 278, 1068 (1997)ADSCrossRefGoogle Scholar
  6. 6.
    J.L. Durant, B.W. Jr, A.L. Lafleur, B.W. Penman, C.L. Crespi, Human cell mutagenicity of oxygenated, nitrated and unsubstituted polycyclic aromatic hydrocarbons associated with urban aerosols. Mutat. Res. 371, 123 (1996)CrossRefGoogle Scholar
  7. 7.
    J.A. Miller, M.J. Pilling, J. Troe, Unravelling combustion mechanisms through a quantitative understanding of elementary reactions. Proc. Combust. Inst. 30, 43–88 (2005)CrossRefGoogle Scholar
  8. 8.
    J.L. Consalvi, F. Liu, J. Contreras, M. Kashif, G. Legros, S. Shuai, J. Wang, Numerical study of soot formation in laminar coflow diffusion flames of methane doped with primary reference fuels. Combust. Flame 162, 1153–1163 (2015)CrossRefGoogle Scholar
  9. 9.
    A.T. Wijayanta, M.S. Alam, K. Nakaso, J. Fukai, Numerical investigation on combustion of coal volatiles under various O2/CO2 mixtures using a detailed mechanism with soot formation. Fuel 93, 670–676 (2012)CrossRefGoogle Scholar
  10. 10.
    G. Jia, M. Yao, H. Liu, P. Zhang, B. Chen, L. Wei, PAHs formation simulation in the premixed laminar flames of TRF with alcohol addition using a semi-detailed combustion mechanism. Fuel 155, 44–54 (2015)CrossRefGoogle Scholar
  11. 11.
    H. Richter, J.B. Howard, Formation of polycyclic aromatic hydrocarbons and their growth to soot-a review of chemical reaction pathways. Prog. Energy Combust. Sci. 26, 565–608 (2000)CrossRefGoogle Scholar
  12. 12.
    Q. Feng, A. Jalali, A.M. Fincham, Y.L. Wang, T.T. Tsotsis, F.N. Egolfopoulos, Soot formation in flames of model biodiesel fuels. Combust. Flame 159, 1876–1893 (2012)CrossRefGoogle Scholar
  13. 13.
    F. Bisetti, G. Blanquart, M.E. Mueller, H. Pitsch, On the formation and early evolution of soot in turbulent nonpremixed flames. Combust. Flame 159, 317–335 (2012)CrossRefGoogle Scholar
  14. 14.
    F. Liu, X. He, X. Ma, Q. Zhang, M.J. Thomson, H. Guo, G.J. Smallwood, S. Shuai, J. Wang, An experimental and numerical study of the effects of dimethyl ether addition to fuel on polycyclic aromatic hydrocarbon and soot formation in laminar coflow ethylene/air diffusion flames. Combust. Flame 158, 547–563 (2011)CrossRefGoogle Scholar
  15. 15.
    S.S. Yoon, S.M. Lee, S.H. Chung, Effect of mixing methane, ethane, propane, and propene on the synergistic effect of PAH and soot formation in ethylene-base counterflow diffusion flames. Proc. Combust. Inst. 30, 1417–1424 (2005)CrossRefGoogle Scholar
  16. 16.
    M. Frenklach, Reaction mechanism of soot formation in flames. Phys. Chem. Chem. Phys. 4, 2028–2037 (2002)CrossRefGoogle Scholar
  17. 17.
    C. Saggese, S. Ferrario, J. Camacho, A. Cuoci, A. Frassoldati, E. Ranzi, H. Wang, T. Faravelli, Kinetic modeling of particle size distribution of soot in a premixed burner-stabilized stagnation ethylene flame. Combust. Flame 162, 3356–3369 (2015)CrossRefGoogle Scholar
  18. 18.
    P. Desgroux, X. Mercier, K.A. Thomson, Study of the formation of soot and its precursors in flames using optical diagnostics. Proc. Combust. Inst. 34, 1713–1738 (2013)CrossRefGoogle Scholar
  19. 19.
    X. Mercier, A. Faccinetto, P. Desgroux, Laser Diagnostics for Selective and Quantitative Measurement of PAHs and Soot (Springer, London, 2013)CrossRefGoogle Scholar
  20. 20.
    W. Karcher, R. Fordham, J. Dubois, P. Glaude, J. Ligthart, Spectral Atlas of Polycyclic Aromatic Compounds (1985)Google Scholar
  21. 21.
    Z. Chi, B.M. Cullum, D.L. Stokes, J. Mobley, G.H. Miller, M.R. Hajaligol, T. Vo-Dinh, Laser-induced fluorescence studies of polycyclic aromatic hydrocarbons (PAH) vapors at high temperatures. Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 57, 1377–1384 (2001)ADSCrossRefGoogle Scholar
  22. 22.
    Z. Chi, B.M. Cullum, D.L. Stokes, J. Mobley, G.H. Miller, M.R. Hajaligol, T. Vo-Dinh, High-temperature vapor detection of polycyclic aromatic hydrocarbon fluorescence. Fuel 80, 1819–1824 (2001)CrossRefGoogle Scholar
  23. 23.
    S. Bejaoui, R. Lemaire, E. Therssen, Analysis of laser-induced fluorescence spectra obtained in spray flames of diesel and rapeseed methyl ester using the multiple-excitation wavelength laser-induced incandescence technique with IR, UV, and visible excitations. Combust. Sci. Technol. 187, 906–924 (2015)CrossRefGoogle Scholar
  24. 24.
    A. Ciajolo, R. Ragucci, B. Apicella, R. Barbella, J.M. De, A. Tregrossi, Fluorescence spectroscopy of aromatic species produced in rich premixed ethylene flames. Chemosphere 42, 835 (2001)ADSCrossRefGoogle Scholar
  25. 25.
    S. Bejaoui, X. Mercier, P. Desgroux, E. Therssen, Laser induced fluorescence spectroscopy of aromatic species produced in atmospheric sooting flames using UV and visible excitation wavelengths. Combust. Flame 161, 2479–2491 (2014)CrossRefGoogle Scholar
  26. 26.
    M. Sirignano, A. Collina, M. Commodo, P. Minutolo, A. D’Anna, Detection of aromatic hydrocarbons and incipient particles in an opposed-flow flame of ethylene by spectral and time-resolved laser induced emission spectroscopy. Combust. Flame 159, 1663–1669 (2012)CrossRefGoogle Scholar
  27. 27.
    S.M. Lee, S.S. Yoon, S.H. Chung, Synergistic effect on soot formation in counterflow diffusion flames of ethylene–propane mixtures with benzene addition. Combust. Flame 136, 493–500 (2004)CrossRefGoogle Scholar
  28. 28.
    Y. Zhang, L. Wang, P. Liu, B. Guan, H. Ni, Z. Huang, H. Lin, Experimental and kinetic study of the effects of CO2 and H2O addition on PAH formation in laminar premixed C2H4/O2/Ar flames. Combust. Flame 192, 439–451 (2018)CrossRefGoogle Scholar
  29. 29.
    P. Liu, Y. Zhang, L. Wang, B. Tian, B. Guan, D. Han, Z. Huang, H. Lin, The chemical mechanism of exhaust gas recirculation on polycyclic aromatic hydrocarbons formation based on LIF measurement. Energy Fuels 32(6), 7112–7124 (2018)CrossRefGoogle Scholar
  30. 30.
    P. Liu, Z. He, G.L. Hou, B. Guan, H. Lin, Z. Huang, The diagnostics of laser-induced fluorescence (LIF) spectra of PAHs in flame with TD-DFT: special focus on five-membered ring. J. Phys. Chem. A 119, 13009 (2015)CrossRefGoogle Scholar
  31. 31.
    B.C. Choi, S.K. Choi, S.H. Chung, Soot formation characteristics of gasoline surrogate fuels in counterflow diffusion flames. Proc Combust Inst 33, 609–616 (2011)CrossRefGoogle Scholar
  32. 32.
    S.K. Choi, B.C. Choi, S.M. Lee, J.H. Choi, The effect of liquid fuel doping on PAH and soot formation in counterflow ethylene diffusion flames. Exp. Therm. Fluid Sci. 60, 123–131 (2015)CrossRefGoogle Scholar
  33. 33.
    L.E. Brady, Handbook of Fluorescence Spectra of Aromatic Molecules (Academic Press, New York, 1971)Google Scholar
  34. 34.
    J.H. Richardson, M.E. Ando, Sub-part-per-trillion detection of polycyclic aromatic hydrocarbons by laser induced molecular fluorescence. Anal. Chem. 49, 955–959 (1977)CrossRefGoogle Scholar
  35. 35.
    B. Apicella, A. Ciajolo, A. Tregrossi, Fluorescence spectroscopy of complex aromatic mixtures. Anal. Chem. 76, 2138 (2004)CrossRefGoogle Scholar
  36. 36.
    F.M. Behlen, D.B. Mcdonald, V. Sethuraman, S.A. Rice, Fluorescence spectroscopy of cold and warm naphthalene molecules: some new vibrational assignments. Cheminform 13, 5685–5693 (1982)Google Scholar
  37. 37.
    A. Nakajima, Solvent effect on the vibrational structures of the fluorescence and absorption spectra of pyrene. J. Catal. 44, 3272–3277 (2006)Google Scholar
  38. 38.
    F.P. Schwarz, S.P. Wasik, Fluorescence measurements of benzene, naphthalene, anthracene, pyrene, fluoranthene, and benzo(e)pyrene in water. Anal. Chem. 48, 524–528 (1976)CrossRefGoogle Scholar
  39. 39.
    F. Ossler, T. Metz, M. Aldén, Picosecond laser-induced fluorescence from gas-phase polycyclic aromatic hydrocarbons at elevated temperatures. I. Cell measurements. Appl. Phys. B 72, 465–478 (2001)ADSCrossRefGoogle Scholar
  40. 40.
    M.J. Castaldi, N.M. Marinov, C.F. Melius, J. Huang, S.M. Senkan, W.J. Pit, C.K. Westbrook, Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame. Symp. Combust. 26, 693–702 (1996)CrossRefGoogle Scholar
  41. 41.
    Y. Wang, A. Raj, S.H. Chung, Soot modeling of counterflow diffusion flames of ethylene-based binary mixture fuels. Combust. Flame 162, 586–596 (2014)CrossRefGoogle Scholar
  42. 42.
    M. Kühni, C. Morin, P. Guibert, Fluoranthene laser-induced fluorescence at elevated temperatures and pressures: implications for temperature-imaging diagnostics. Appl. Phys. B 102, 659–671 (2011)ADSCrossRefGoogle Scholar
  43. 43.
    M. Orain, P. Baranger, C. Ledier, J. Apeloig, F. Grisch, Fluorescence spectroscopy of kerosene vapour at high temperatures and pressures: potential for gas turbines measurements. Appl. Phys. B 116, 729–745 (2014)ADSCrossRefGoogle Scholar
  44. 44.
    P. Klán, J. Wirz, Photochemistry of organic compounds: from concepts to practice. Energy Build. 35, 933–940 (2009)Google Scholar
  45. 45.
    C. Schulz, V. Sick, Tracer-LIF diagnostics: quantitative measurement of fuel concentration, temperature and fuel/air ratio in practical combustion systems. Prog. Energy Combust. Sci. 31, 75–121 (2005)CrossRefGoogle Scholar
  46. 46.
    B.H. Cheung, R.K. Hanson, 3-pentanone fluorescence yield measurements and modeling at elevated temperatures and pressures. Appl. Phys. B 106, 755–768 (2012)ADSCrossRefGoogle Scholar
  47. 47.
    M.C. Thurber, F. Grisch, B.J. Kirby, M. Votsmeier, R.K. Hanson, Measurements and modeling of acetone laser-induced fluorescence with implications for temperature-imaging diagnostics. Appl. Opt. 37, 4963–4978 (1998)ADSCrossRefGoogle Scholar
  48. 48.
    J. Koch, Fuel tracer photophysics for quantitative planar laser-induced fluorescence, Dissertation Abstracts International, vol. 66–04, Section: B, p. 2273; Adviser: Ronald K. Hans (2005)Google Scholar
  49. 49.
    D.A. Rothamer, Development and application of infrared and tracer-based planar laser-induced fluorescence imaging diagnostics, vol. 68, No. 12 (2008)Google Scholar
  50. 50.
    M. Orain, P. Baranger, B. Rossow, F. Grisch, Fluorescence spectroscopy of naphthalene at high temperatures and pressures: implications for fuel-concentration measurements. Appl. Phys. B 102, 163–172 (2011)ADSCrossRefGoogle Scholar
  51. 51.
    C. Baumhakl, S. Karellas, Tar analysis from biomass gasification by means of online fluorescence spectroscopy. Opt. Lasers Eng. 49, 885–891 (2011)CrossRefGoogle Scholar
  52. 52.
    S.A. Kaiser, M.B. Long, Quantitative planar laser-induced fluorescence of naphthalenes as fuel tracers. Proc. Combust. Inst. 30, 1555–1563 (2005)CrossRefGoogle Scholar
  53. 53.
    R. Sun, N. Zobel, Y. Neubauer, C.C. Chavez, F. Behrendt, Analysis of gas-phase polycyclic aromatic hydrocarbon mixtures by laser-induced fluorescence. Opt. Lasers Eng. 48, 1231–1237 (2010)CrossRefGoogle Scholar
  54. 54.
    M. Suto, X. Wang, J. Shan, L.C. Lee, Quantitative photoabsorption and fluorescence spectroscopy of benzene, naphthalene, and some derivatives at 106–295 nm. J. Quant. Spectrosc. Radiat. Trans. 48, 79–89 (1992)ADSCrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Yiran Zhang
    • 1
  • Lijun Wang
    • 1
  • Peng Liu
    • 2
  • Youping Li
    • 1
  • Reggie Zhan
    • 1
  • Zhen Huang
    • 1
  • He Lin
    • 1
    Email author
  1. 1.Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical EngineeringShanghai Jiao Tong UniversityShanghaiChina
  2. 2.Clean Combustion Research CenterKing Abdullah University of Science and Technology (KAUST)ThuwalSaudi Arabia

Personalised recommendations