Emilio J. Gallegos

Relationship Between Petroleum Composition and Depositional Environment of Petroleum Source Rocks

Crude oils of nonmarine source can be distinguished from those of marine shale source and from oils originating in marine carbonate sequences by using a battery of geochemical parameters, as demonstrated with a sample suite of nearly 40 oils. A novel parameter based on the presence of C30 steranes in the oil was found to be a definitive indication of a contribution to the source from marine-derived organic matter. A second novel parameter based on monoaromatized steroid distributions was effective in helping to distinguish nonmarine from marine crudes and can be used to gauge relative amounts of higher plant input to oils within a given basin. Sterane distributions were similarly useful for detecting higher plant input but were less effective than monoaromatize steroid distributions for making marine versus nonmarine distinctions. Concentrations of high molecular-weight paraffin can also be effective nonmarine indicators but are influenced by maturation and biodegradation processes. Certain algal-derived nonmarine oils may show little high molecular-weight paraffin response. Oils from carbonate sources (with a few exceptions) can be distinguished by having low pristane-phytane ratios, low carbon preference indexes, and high sulfur contents. Gammacerane indexes and carbon isotope ratios of the whole crude are not effective in distinguishing these types of environmental differences on a global basis.

Identification of an extended series of tricyclic terpanes in petroleum

A series of tricyclic terpanes from C19 to C45 has been identified in petroleum by gas chromatographic mass spectroscopic (GCMS) analysis. This discovery extends the previously known homologous series reported from C19 to C30. A method of preparation of a tricyclic terpane concentrate is described which facilitates tricyclic terpane analysis by the GCMS m/z 191 fragment. Metastable scanning GCMS is described as an additional method for characterization of the tricyclic terpanes.

Analysis and occurrence of C26-steranes in petroleum and source rocks

Abstract The C26-steranes previously reported in oils and source rocks (MOLDOWAN et al., 1985) have been identified as 21-, 24-, and 27-norcholestanes (1A, 1B, and 1C). Various 24-norcholesterols or stanols, possible precursors for the 24-norcholestanes, occur widely at low levels in marine invertebrates and some algae, and 24-norcholestanes occur in marine petroleums of Tertiary through Paleozoic age. There are reports of 27-norcholesterols and stanols in recent sediments, but the precursor organisms have not been identified. The natural occurrence of the 21-norcholestane structure is unprecedented. Unlike 24- and 27-norcholestane, 21-norcholestane is in low concentration or absent in immature rocks and increases substantially relative to the other C26-steranes in thermally mature rocks, oils, and condensates. This suggests an origin involving thermal degradation of a higher molecular weight steroid. The ratio of 21-norcholestane to the total C26-steranes is shown to be an effective maturity parameter in a series of Wyoming (Phosphoria source) and California (Monterey source) oils. Molecular mechanics MM2 steric energy calculations indicate a relative stability order of 21 ⪢ 27 > 24- norcholestane for the major stereoisomers. Authentic 21-, 24-, and 27-nor-5α-cholestanes and 24- and 27-nor-5β-cholestanes were synthesized and subjected to catalytic isomerization over Pd/C to yield the full suite of stereoisomers for each. In immature rocks the 5α,14α,17α(H),20R isomers predominate. Mixtures of 24- and 27-norcholestane in oils and mature rocks show a familiar elution pattern of four major peaks presumed to be 14α,17α(H),20S, 14β,17β(H),20R, 14β,17β(H),20S, and 14α,17α(H),20R in order of elution, as well as putative 20S and 20R rearranged steranes [13β,17α(H)-diasteranes]. However, the 21-norcholestanes are represented by a single peak in mature sediments under normal GC conditions, which is shown to consist of a major 14β,17α(H) peak and a minor 14α,17α(H) peak using an extended injection-temperature-hold-time gas Chromatographic technique.