Molecular characterization of petroporphyrins in crude oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

R. P. Rodgers, C. L. Hendrickson, Mark Emmett, A. G. Marshall, M. Greaney, K. Qian

Research output: Contribution to journalArticle

82 Citations (Scopus)

Abstract

Petroporphyrin compositional analysis of a heavy crude oil has been realized by isolation and subsequent ESI-FT-ICR mass spectrometric analysis of the porphyrin-containing fractions. Vanadium octaethyl (V=O(II)OEP) and nickel octaethyl (Ni(II)OEP) porphyrin standards were analyzed to determine favorable electrospray ionization conditions and provide insight as to the molecular species present (e.g., adducts, multimers). Standard V=O(II)OEP and Ni(II)OEP solutions revealed the presence of both monomer and dimer species with a greater relative abundance of monomers. In contrast, mass spectral analysis of a porphyrin fraction from Cerro Negro crude oil was dominated by dimeric species. MS3 analysis identified a dioctylphthalate (DOP) contaminant, likely introduced during fractionation of the crude oil. DOP-porphyrin complexes and porphyrin-porphyrin dimers were then identified. Infrared multiphoton dissociation (IRMPD) of dimeric species produced the corresponding monomers with minimal fragmentation. The monomeric petroporphyrins were analyzed to reveal the metal (Ni(II) or V=O(II)), porphyrin type (e.g., etio vs. DPEP), and distribution of alkylation.

Original languageEnglish (US)
Pages (from-to)546-551
Number of pages6
JournalCanadian Journal of Chemistry
Volume79
Issue number5-6
DOIs
StatePublished - 2001
Externally publishedYes

Fingerprint

Cyclotron resonance
Electrospray ionization
Porphyrins
Petroleum
Mass spectrometry
Fourier transforms
Crude oil
Ions
Monomers
Dimers
Vanadium
Alkylation
Fractionation
Nickel
Spectrum analysis
Metals
Impurities
Infrared radiation

Keywords

  • Electrospray ionization
  • Fourier transform
  • FT-ICR
  • FTMS
  • ICR
  • Ion cyclotron resonance
  • Mass spectrometry
  • Petroleum
  • Petroporphyrin
  • Porphyrin

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Molecular characterization of petroporphyrins in crude oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. / Rodgers, R. P.; Hendrickson, C. L.; Emmett, Mark; Marshall, A. G.; Greaney, M.; Qian, K.

In: Canadian Journal of Chemistry, Vol. 79, No. 5-6, 2001, p. 546-551.

Research output: Contribution to journalArticle

Rodgers, R. P. ; Hendrickson, C. L. ; Emmett, Mark ; Marshall, A. G. ; Greaney, M. ; Qian, K. / Molecular characterization of petroporphyrins in crude oil by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. In: Canadian Journal of Chemistry. 2001 ; Vol. 79, No. 5-6. pp. 546-551.
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