Abstract
Microprobe two-step laser desorption/laser ionization mass spectrometry (μL2MS) and gas chromatography/mass spectrometry (GC/MS) were used to analyze polycyclic aromatic hydrocarbons (PAHs) in ancient terrestrial rocks. μL2MS provides an in situ analysis of very small samples, records the PAHs with no isomer information, and gives quantitative data on the degree of alkylation of a given PAH series over the complete mass range. GC/MS provides isomer separation and quantitation of PAHs in bitumen but not kerogen, and is limited by sample size. Combination of these techniques allows analysis of very small samples by μL2MS with GC/MS confirmation of isomer distributions of the solvent extractable components (bitumen). It was found that the concentration of bitumen within the rock samples affects the PAH alkylation signal for μL2MS. At low bitumen concentrations μL2MS can produce pyrolysis products from kerogen that is present; however, as bitumen concentrations increase, the PAH distribution from bitumen dominates the signal.
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Blumer, M. Sci. Am. 1976, 243, 35–45.
Hoffman, D.; Wydner, E. L. In Air Pollution Vol. II; Stern, A., Ed.; New York, 1968; pp 187–242.
Orr, W. L.; Grady, J. R. Geochim. Cosmochim. Acta 1967, 31, 1201–1209.
Brown, F. S.; Baedecker, M. J.; Nissenbaum, A.; Kaplan, I. R. Gecohim. Cosmochim. Acta 1972, 36, 1185–1203.
Borneff, J.; Selenka, F.; Kunte, H.; Mazimos, A. Environ. Res. 1968, 2, 22–29.
Graef, W.; Diehl, H. Arch. Hyg. Bacteriol. 1966, 150, 49–59.
Hancock, J. L.; Applegate, H. G.; Dodd, J. D. Atmos. Environ. 1970, 4, 363–370.
Brisou, J. C. R. Soc. Biol. 1969, 163, 772–774.
Knorr, M.; Schenk, D. Arch. Hyg. Bakteriol. 1968, 152, 282–285.
De Lima-Zanghi, C. Cah. Oceanogr. 1968, 20, 203–216.
Mallet, L.; Tissier, M. C. R. Soc. Biol. 1969, 163, 63–65.
Niaussat, P.; Mallet, L.; Ottenwaelder, J. C. R. Acad. Sci. (Paris) 1969, 268D, 1109–1112.
Niaussat, P.; Auger, C.; Mallet, L. C. R. Acad. Sci. (Paris) 1970, 270D, 1042–1045.
ZoBell, C. E. N. Z. Oceanogr. Inst. Rec. 1959, 3, 39–47.
Hase, A.; Hites, R. A. Geochim. Cosmochim. Acta 1976, 40, 1141–1143.
Grimmer, G.; Duevel, D. Z. Naturforsch. Teil B 1970, 25, 1171–1175.
Radke, M.; Welte, D. H.; Willsch, H. Geochim. Cosmochim. Acta 1982, 46, 1–10.
Willsch, H.; Radke, M. Polycyclic Aromat. Compd. 1995, 7, 231–251.
Radke, M. Mar. Petrol. Geol. 1988, 5, 224–236.
Ramanampisoa, L.; Radke, M. J. Petrol Geol. 1992, 15, 379–396.
Budzinski, H.; Garrigues, P.; Connan, J.; Devillers, J.; Domine, D.; Radke, M.; Oudin, J. L. Geochim. Cosmochim. Acta 1995, 59, 2043–2056.
Requejo, A. G.; Sassen, R.; McDonald, T.; Denoux, G.; Kennicutt, M. C.; Brooks, J. M. Org. Geochem. 1996, 24, 1017–1033.
Peters, K. E.; Moldowan, J. M. The Biomarker Guide, Prentice-Hall, Inc.: New Jersey, 1993; p 7.
Hahn, J. H. Ph.D. Thesis, Stanford University, 1988.
Zenobi, R.; Philippoz, J. M.; Buseck, P. R.; Zare, R. N. Science 1989, 246, 1026–1029.
McKay, D. S.; Gibson, E. K.; Thomas-Keprta, K. L.; Vali, H.; Romanek, C. S.; Clemett, S. J.; Chillier, X. D. F.; Maechling, C. R.; Zare, R. N. Science 1996, 273, 924–930.
Kovalenko, L. J.; Maechling, C. R.; Clemett, S. J.; Philippoz, J. M.; Zare, R. N.; Alexander, C. M. Anal. Chem. 1992, 64, 682–690.
Clemett, S. J.; Maechling, C. R.; Zare, R. N.; Swan, P. D.; Walker, R. M. Science 1993, 262, 721–725.
Clemett, S. J. Ph.D. Thesis, Stanford University, 1996.
Dale, M. J.; Jones, A. C.; Pollard, S. J. T.; Langridge-Smith, P. R. R. Analyst 1994, 119, 571–578.
Dale, M. J.; Jones, A. C.; Pollard, S. J. T.; Langridge-Smith, P. R. R.; Rowley, A. G. Environ. Sci. Technol. 1993, 27, 1693–1695.
Gillette, J. S.; Luthy, R. G.; Clemett, S. J.; Zare, R. N. Environ. Sci. Tecnol. 1999, 33, 1185–1192.
Ghosh, U.; Gillette, J. S.; Luthy, R. G.; Zare, R. N. Environ. Sci. Technol. 2000, 34, 1729–1736.
Hankin, S. M.; John, P. Anal. Chem. 1999, 71, 1100–1104.
Haefliger, O. P.; Bucheli, T. D.; Zenobi, R. Environ. Sci. Technol. 2000, 34, 2178–2183.
Zhan, Q.; Voumard, P.; Zenobi, R. Rapid Commun. Mass Spectrom. 1995, 9, 119–127.
Zhan, Q.; Zenobi, R.; Wright, S. J.; Langridge-Smith, P. R. R. Macromolecules 1996, 29, 7865–7871.
Wright, S. J.; Dale, M. J.; Langridge-Smith, P. R. R.; Zhan, Q.; Zenobi, R. Anal. Chem. 1996, 68, 3585–3594.
Engelke, F.; Hahn, J. H.; Henke, W.; Zare, R. N. Anal. Chem. 1987, 59, 909–912.
Dale, M. J.; Costello, K. F.; Jones, A. C.; Langridge-Smith, P. R. R. J. Mass Spectrom. 1996, 31, 590–601.
Dale, M. J.; Jones, A. C.; Langridge-Smith, P. R. R.; Costello, K. F.; Cummings, P. G. Anal. Chem. 1993, 65, 793–801.
Dale, M. J.; Zhan, Q.; Zenobi, R.; Costello, K.; Langridge-Smith, P. R. R. Anal. Methods Instr. 1995, 2, 101–105.
Haefliger, O. P.; Zenobi, R. Anal. Chem. 1998, 70, 2660–2665.
Clemett, S. J.; Zare, R. N. In Molecules in Astrophysics: Probes and Processes; E. F. van Dishoeck, Ed. Kluwer Academic Press: London, 1997; p 313.
Cowin, J. P.; Auerbach, D. J.; Becker, C.; Wharton, L. Surf. Sci. 1978, 78, 545–564.
Grob, K. Chromatographia 1974, 7, 94–98.
Summons, R. E.; Powell, T. G.; Boreham, C. B. Geochim. Cosmochim. Acta 1988, 52, 1747–1763.
Logan, G. A.; Hinman, M.; Walter, M. R.; Summons, R. E. Geochim. Cosmochim. Acta 2001, in press.
Summons, R. E.; Janhke, L. L.; Hope, J.; Logan, G. A. Nature 1999, 400, 554–557.
Brocks, J. J.; Logan, G. A.; Buick, R.; Summons, R. E. Science 1999, 285, 1033–1036.
Eldridge, C. S.; Williams, N.; Walshe, J. L. Econ. Geol. 1993, 88, 1–26.
Baross, J. A.; Hoffman, S. E. Origins Life Evol. Biosphere 1985, 15, 327–345.
Fisk, M. R.; Giovannoni, S. J. J. Geophys. Res. (Planets) 1999, 104, 11805–11815.
Shock, E. L. Mineral. Mag. 1998, 62A, 1394–1395.
Zenobi, R.; Zare, R. N. In Advances in Multi-Photon Processes and Spectroscopy; Lin, S. H., Ed.; World Scientific Publishing Co.; 1991; Vol. VII, pp 1–168.
Wiley, W. C.; McLaren, I. H. Rev. Sci. Instrum. 1955, 26, 1150–1157.
Tissot, B. P.; Welte, D. H. Petroleum Formation and Occurrence; Springer-Verlag: Berlin, 1984; pp 509, 522.
Hahn, J. H.; Zenobi, R.; Zare, R. N. J. Am. Chem. Soc. 1987, 109, 2842–2843.
Greenwood, P. F.; Zhang, E.; Vastola, F. J.; Hatcher, P. G. Anal. Chem. 1993, 65, 1937–1946.
Greenwood, P. F.; Sherwood, N. APEA Journal 1995, 35, 633–645.
Greenwood, P. F.; Sherwood, N.; Willett, G. D. J. Anal. Appl. Pyrol. 1995, 31, 177–202.
Greenwood, P. F.; George, S. C.; Wilson, M. A.; Hall, K. J. J. Anal. Appl. Pyrol. 1996, 38, 101–118.
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Mahajan, T.B., Plows, F.L., Gillette, J.S. et al. Comparison of microprobe two-step laser desorption/laser ionization mass spectrometry and gas chromatography/ mass spectrometry studies of polycyclic aromatic hydrocarbons in ancient terrestrial rocks. J Am Soc Spectrom 12, 989–1001 (2001). https://doi.org/10.1016/S1044-0305(01)00279-3
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DOI: https://doi.org/10.1016/S1044-0305(01)00279-3