PETROLEOMICS BY ESI(-) FT-ICR MS AS A TOOL TO ASSESS SOURCE AND

THERMAL MATURITY OF BRAZILIAN CRUDE OILS

Y.S. Rocha1, A.L.D. Spigolon1, W.L. Bastos1, J.P. Lopes1, F.G. Leal1, J.V.P. Guzzo1, M.D.,
Rangel1, B.G. Vaz2, R.C.L. Pereira2, J.G. Mendonça Filho3
1
Petrobras R&D Center; ²Federal University of Goiás; 3Federal University of Rio de Janeiro

Introduction

Geochemical assessments of crude oil samples are typically carried out to identify their origins
(depositional environments), thermal evolution level of their source rocks and to evaluate
possible post-accumulation alterations such as biodegradation. Crude oils consist
predominantly of hydrocarbon compounds, comprising paraffin, cycloalkanes, and aromatics
(~85%), followed by polar compounds (~15%), such as nitrogen-, sulfur-, oxygen-containing
compounds (NSO compounds). Even though NSO compounds are present in smaller
concentrations, they can be used to assess the mechanisms of generation, migration, and
alteration of crude oils.

The ultrahigh mass resolution and accuracy of FT-ICR MS are ideal for the analysis of complex
heteroatomic compounds, allowing for the assignment of detected masses to chemical formulas
(Marshall et al., 2007). When coupled with the electrospray ionization technique (ESI) the
detailed composition of selective polar species can be resolved from the pseudo-molecular ions
produced (Qian et al., 2001). Ultrahigh resolution mass spectrometry has characterized
thousands of hydrocarbon and polar species in petroleum and related products.

In this study, we show the application of ESI(-) FT-ICR MS results in association with
traditional geochemical parameters to evaluate thermal maturity, source input and depositional
environments from oil samples.

Results and Discussion

Using ESI FT-ICR MS in the negative mode, we track the changes on polar compounds
controlled by thermal maturity. This technique allowed us to visualize and assess compositional
variability for a sub-group of heteroatomic compounds. Sulfur-containing compounds are
destroyed with ongoing maturity, and oxygen-containing compounds progressively decrease
due to decarboxylation and dehydration reactions. In contrast, nitrogen-containing compounds
increase at high maturity levels. DBE (double bound equivalent) values increase, expressing
the aromaticity and condensation of their constituents. The carbon number distribution shifts
progressively toward the lower carbon number region, which indicates an enrichment of lighter
compounds in the expelled oils and the occurrence of substantially dealkylated species in the
polar fraction as maturity increases. The carbon number distribution of DBE`s 5 and 6 for the
O2 class (related to steranoic and hopanoic acids respectively) decrease with ongoing maturity.
The maturity-related changes of the acidic O2 compounds for the expelled oil samples enable
us to create six regressions to be used as new maturity parameters covering the full range of oil
generation (Rocha et al., 2018a).

Lacustrine-derived oils seems to be enriched in Nx compounds, while the dominance of Ox

compounds is observed in marine-derived oils. The most abundant class detected in crude oils

29th International Meeting on Organic Geochemistry (IMOG)

1–6 September 2019, Gothenburg, Sweden
studied was N1, followed by O1, O2, and N1O2 with remarkable differences between marine
and lacustrine oils distribution. Kerogen type plays an important role in the heteroatomic
profile of the crude oils analyzed. Organic matter from kerogen Type I has high H/C atomic
ratio and low oxygen content, while organic matter from Type II kerogen contains higher O/C
atomic ratio and high abundance of carboxylic acid groups and ester groups (Vandenbroucke
and Largeau, 2007). Such differences result in a clear separation based on polar species found
in marine and lacustrine oils generated from Type I and Type II kerogens. Oil-oil correlations
show significant differences between the oils, basically on DBE distributions of selected
heteroatomic classes of crude oils evaluated, allowing a quick geochemical assessment of their
origin (Rocha et al., 2018b).

Conclusions

The use of negative ESI FT-ICRMS technique is a reliable and valuable tool for performing
geochemical assessments from NSO compounds pattern. In association with geochemical
traditional tools, it is possible to achieve a full comprehension of crude oil composition, besides
obtaining information about origin and maturity parameters.

Figure 1 Petroleomics as a tool for geochemical assessment of crude oil samples to identify
their depositional environments (in green) and thermal evolution level (in yellow).

References

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29th International Meeting on Organic Geochemistry (IMOG)

1–6 September 2019, Gothenburg, Sweden