http://dx.doi.org/10.4322/sc.2012.010

 

La cromatografía de gases acoplada a espectrometría de masas como herramienta de alta selectividad para caracterizar fósiles químicos en el petróleo

Stashenko, Elena E.; Martínez, Jairo R.

Palavras-chave: Cromatografía de gases, GC-MS, espectrometría de masas tándem, SIM, MRM, biomarcadores.

Resumo La determinación de fósiles químicos (biomarcadores) en el petróleo constituye un reto analítico formidable, porque requiere la detección y la cuantificación de moléculas específicas, presentes en cantidades a nivel de trazas, en mezclas de hidrocarburos altamente complejas. En este artículo, se resaltan algunos resultados de importancia para la geoquímica orgánica, que han sido posibles gracias al uso de la espectrometría de masas como sistema de detección, altamente sensible y selectivo, en conjunto con la alta resolución que alcanzan la cromatografía de gases monodimensional y la cromatografía de gases completa (GC × GC). Se han seleccionado ejemplos representativos de estudios recientes de biomarcadores en la geoquímica ambiental y en la geoquímica del petróleo.


Referências Bibliográficas

1. Speight J. The chemistry and technology of petroleum. Marcel Dekker, Inc. New York, 1991, 760 p.
2. Streibl M, Herout V. Terpenoids-especially oxygenated mono-, sesqui-, di-, and triterpenoids. In: Eglinton G, Murphy MTJ, editors. Organic geochemistry: Methods and results. Berlin: Springer-Verlag; 1969. p. 402-424.
3. Eglinton G, Calvin M. Chemical fossils. Scientific American 1967; 216:32-43.
4. Demaison G, Bradley H. Genetic classification of petroleum system. AAPG Bulletin 1991; 75(10):1626‑1643.
5. Taylor RF. Bacterial triterpenoids. Microbiological Reviews 1984; 48:181-198.
6. Volkman JK. A review of sterol markers for marine and terrigenous organic matter. Organic Geochemistry 1986; 9(2):83-99. http://dx.doi. org/10.1016/0146-6380(86)90089-6
7. Gaines S, Eglinton G, Rullkötter J. Echoes of life – What fossil molecules reveal about earth history. New York: Oxford University Press; 2008.
8. Peters KE, Walters CC, Moldowan JM. The Biomarker Guide. 2nd ed. New York: Cambridge University Press; 2005.
9. Simoneit B. A review of current applications of mass spectrometry for biomarker/molecular tracer elucidations. Mass Spectrometry Reviews 2005; 24:719‑765. PMid:15534872.
10. Medeiros PM, Simoneit BR. Gas chromatography coupled to mass spectrometry for analyses of organic compounds and biomarkers as tracers for geological, environmental, and forensic research. Journal of Separation Science 2007; 30:1516-1536. PMid:17623433.
11. Fernández-Varela R, Andrade JM, Muniategui S, Prada D. Selecting a reduced suite of diagnostic ratios calculated between petroleum biomarkers and polycyclic aromatic hydrocarbons to characterize a set of crude oils. Journal of Chromatography A 2010; 1217(52):8279-8289. PMid:21081235. http:// dx.doi.org/10.1016/j.chroma.2010.10.043
12. Scholz-Böttcher B, Ahlf S, Vázquez-Gutiérrez F, Rullkötter J. Natural vs. anthropogenic sources of hydrocarbons as revealed through biomarker analysis: A case study in the southern Gulf of Mexico. Boletín de la Sociedad Geológica Mexicana 2009; 61(1):47-56.
13. Stashenko E, Martínez J. GC-MS: Más de un analizador de masas, ¿para qué? Scientia Chromatographica. 2010;2(4):33-59.
14. Gómez-Carracedo M, Ferré J, Andrade J, Fernández-Varela R, Boqué R. Objective chemical fingerprinting of oil spills by partial least-squares discriminant analysis. Analytical and Bioanalytical Chemistry 2012; 403(7):2027-2037. http://dx.doi. org/10.1007/s00216-012-6008-5
15. Christensen J, Tomasi G, Hansen A. Chemical fingerprinting of petroleum biomarkers using time warping and PCA. Environmental Science and Technology 2005; 39:255-260. http://dx.doi. org/10.1021/es049832d
16. Wang Z, Fingas M, Li K. Fractionation of ASMB oil, identification and quantitation of aliphatic, aromatic and biomarker compounds by GC/FID and GC/MSD. Journal of Chromatographic Science 1994 32:361-366 (Parte I), 367-382 (Parte II). http://dx.doi.org/10.1093/ chromsci/32.9.361
17. Nytoft H, Bojesen-Koefoed J, Christiansen F, Fowler M. Oleanane or lupane? Reappraisal of the presence of oleanane in Cretaceous-Tertiary oils and sediments. Organic Geochemistry 2002; 33:1225-1240. http:// dx.doi.org/10.1016/S0146-6380(02)00138-9
18. Nguyen T, Bocherens H, Mariotti A, Baudin F, Pons D, Broutin J et al. Ecological distribution of Cenomanian terrestrial plants based on 13C/12C ratios. Palaeogeography, Palaeoclimatology Palaeoecology 1999; 145:79-93. http://dx.doi. org/10.1016/S0031-0182(98)00092-3
19. Hayes T, Freeman K, Popp B, Hoham C. Compound specific isotope analyses: a novel tool for reconstruction of biogeochemical processes. Organic Geochemistry 1990; 16:1115-1128. PMid:11540919. http://dx.doi.org/10.1016/0146-6380(90)90147-R
20. Cortes J, Rincon J, Jaramillo J, Philp P, Allen J. Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin, Colombia. Journal of South American Earth Sciences 2010; 29;198-213.
21. Kinghorn R, Marriott P, Dawes P. Design and implementation of comprehensive gas chromatography with cryogenic modulation. Journal of Separation Science 2000; 23(3):245-252. http:// dx.doi.org/10.1016/j.jsames.2009.03.010
22. Tran T, Logan G, Grosjean E, Ryan D, Marriott P. Use of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry for the characterization of biodegradation and unresolved complex mixtures in petroleum. Geochimica et Cosmochimica Acta 2010; 74:6468-6484. http://dx.doi. org/10.1016/j.gca.2010.08.024
23. Ventura G, Kenig F, Reddy C, Frysinger G, Nelson R, Van Mooy B et al. Analysis of unresolved complex mixtures of hydrocarbons extracted from Late Archean sediments by comprehensive two-dimensional gas chromatography (GCxGC). Organic Geochemistry 2008; 39(7):846-867. http:// dx.doi.org/10.1016/j.orggeochem.2008.03.006
24. Ventura G, Raghuraman B, Nelson R, Mullins O, Reddy C. Compound class oil fingerprinting techniques using comprehensive two-dimensional gas chromatography (GCxGC). Organic Geochemistry 2010; 41:1026-1035. http://dx.doi.org/10.1016/j.orggeochem.2010.02.014
25. Oliveira C, Ferreira A, Oliveira C, Azevedo D, Santos Neto EV, Aquino Neto FR. Biomarkers in crude oil revealed by comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry: Depositional paleoenvironment proxies. Organic Geochemistry 2012; 46:154-164. http://dx.doi. org/10.1016/j.orggeochem.2012.03.002
26. Ávila B, Aguiar A, Gomes A, Azevedo D. Characterization of extra heavy gas oil biomarkers using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. Organic Geochemistry 2010; 41:863-866. http://dx.doi. org/10.1016/j.orggeochem.2010.03.008
27. Aguiar A, Silva A, Azevedo D, Aquino F. Application of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry to biomarker characterization in Brazilian oils. Fuel 2010; 89:2760-2768. http://dx.doi.org/10.1016/j. fuel.2010.05.022
28. Eiserbeck C, Nelson R, Grice K, Curiale J, Reddy C. Comparison of GC-MS, GC-MRM-MS, and GC x GC to characterise higher plant biomarkers in Tertiary oils and rock extracts. Geochimica et Cosmochimica Acta 2012; 87:299-322.
29. Chiaberge S, Fiorani T, Cesti P. Methyldibenzothiophene isomer ratio in crude oils: Gas chromatography tandem mass spectrometry analysis. Fuel Processing Technology 2011; 92:2196- 2201.. http://dx.doi.org/10.1016/j.fuproc.2011.07.011
30. Liang Q, Xiong Y, Fang C, Li Y. Quantitative analysis of diamondoids in crude oils using gas chromatographytriple quadrupole mass spectrometry. Organic Geochemistry 2012; 43:83-91. http://dx.doi. org/10.1016/j.orggeochem.2011.10.008.