H004

Applying Fluid Inclusions Mass Spectrometry to

Support Exploratory Plays, Marañon Basin, Peru
A Chalco* (Cepsa)

SUMMARY
The interpretation of fluid inclusions mass spectrometry analysis from core plug samples of the
Ungumayo-1X exploratory well and to core plug samples from a neighbouring oilfield in the Marañon
Basin (Peru), suggest the potential presence of an hydrocarbon accumulation, either updip of the
Ungumayo-1X well or at underlying Early Cretaceous undrilled reservoir, opening the opportunity to test a
new play in the area.

72nd EAGE Conference & Exhibition incorporating SPE EUROPEC 2010

Barcelona, Spain, 14 - 17 June 2010
Introduction

The Ungumayo is a four-way closure structure located at the central part of the Marañon Basin
foredeep, inside an oil province extending through Colombia, Ecuador and Peru (Figure 1). A well
drilled in 1974 into the southwest flank of the structure, found wet the traditional Campanian-
Maastrichtian and Coniacian sandstone reservoirs, but encountered poor oil shows in a Cenomanian
sandstone. A regional re-evaluation of Marañon Basin well data highlights the untested potential of
the Early Cretaceous clastic reservoirs.

The interpretation of the mass spectrometry analysis of fluid inclusions from the Cenomanian
sandstone drilled by the Ungumayo-1X well are compared to the fluid inclusions of a Coniacian
sandstone reservoir from a neighbouring oilfield, to support a proposal to re-drill the Ungumayo
structure updip of the previous well, into deeper objectives.
For a details on the Northern Marañon Basin petroleum geology and its petroleum system, please
refer to Aleman et al (1999).

Figure 1 Location of the Ungumayo-1X well and its neighbouring oilfield, Marañon Basin, Peru.

Workflow and Interpretation methods

All the core plugs were screened for fluid inclusions, using thin section petrography, ultraviolet
fluorescence and microthermometry.

The selected samples (three from the Ungumayo-1X and two from the neighbouring field), were
crushed to obtain the bulk chemical composition of the volatiles contained in the fluid inclusions by
quadrupole mass spectrometric analysis. This type of analysis can reliably identify ions from
inorganic gases, dry organic gases, water soluble hydrocarbons, C1 to C13 petroleum compounds and
sulphur compounds, without fractionation or evaporative loss problems during sampling.

72nd EAGE Conference & Exhibition incorporating SPE EUROPEC 2010

Barcelona, Spain, 14 - 17 June 2010
The results are presented as a series of atomic mass ratios (m/z) against depth or as the millivolt
response of 16 different ions, against depth (“mass spectra”). For a detailed discussion of the
laboratory workflow, data consistency and calibration procedures of the mass spectra please refer to
the website www.fittulsa.com.

The interpretation of the mass spectrometry results has two parts:

• The identification of specific compounds.

• The identification of patterns in the mass spectra within the local geologic context.

Specific compounds interpretation

Specific compounds are influenced by the genesis, saturation and size of its host fluid inclusion, by
the composition of the original fluid and by its residence time in the pore system. Chemical ratios can
be employed to reduce these influences and to highlight subtle trends. The most useful compounds
identified were:

Methane (m/z 15): Contains minor contributions from other Paraffins. It’s associated to oil or gas
migration zones or wet zones containing dissolved gas.

Alkylated Naphtenes (m/z 97): Derived from Napthenes with a methyl chain. High concentrations are
encountered in fluid inclusions containing oil or condensate.

Benzene (m/ 78): Associated to fluid inclusions at a petroleum column interval or close to a
hydrocarbon accumulation.

Acetic Acid (m/z 60): Derives from mature coaly source rocks, thermal cracking of liquid
hydrocarbons accumulations, or proximity to a hydrocarbon accumulation.

CS2 and C6+hydrocarbons (m/z 22): Associated to biodegraded hydrocarbons.

Mass spectra pattern interpretation

The mass spectra of any subsurface fluid contain multiple interfering ions. Although the absolute
abundance for any specific compound cannot be calculated, distinctive patterns can be identified for
some major classes of chemical compounds:

Non hydrocarbon enriched mass spectra (m/z 2 to 46): Its tallest peaks are water (m/z 16 to18 and 28)
and carbon dioxide (m/z 44 to 49), respectively. Its peak clusters are on m/z 15, 28, 42 and 55.

Hydrocarbon gas enriched mass spectra (m/z 13 to 16, 26 to 30, 39 to 44, 55 to 57): It’s composed
mostly of C1 to C5 hydrocarbon compounds, with the occasional presence of C6 to C8 hydrocarbons,
belonging to short chain Paraffins and Napthenes. Its peak clusters are m/z 12 to 30 and m/z 37 to 46.

Liquid range hydrocarbons (C7 to C13+) enriched mass spectra (m/z 95 to 185).

Water soluble hydrocarbons enriched mass spectra: Its tallest peaks are for Formic Acid (m/z 46),
Acetic acid (m/z 60), Propionic Acid (m/z 74), Benzene (m/z 78), Toluene (m/z 92). It’s peak clusters
are m/z 60, 78, 91 and 105.

Sulphur compounds enriched mass spectra. H2S (m/z 34), COS (m/z 60), S2 or SO2 (M/Z 64) and CS2
(m/z 76).

The overlap of the gas enriched, liquids enriched and water soluble hydrocarbon patterns is very
common.

72nd EAGE Conference & Exhibition incorporating SPE EUROPEC 2010

Barcelona, Spain, 14 - 17 June 2010
Ungumayo-1X well specific compounds interpretation

The Ungumayo-1X samples have a similar response to Methane (m/z 15) than that of the two oilfield
samples, a slightly smaller response for Alkylated Napthenes (m/z 97) and CS2 and C6+
hydrocarbons (m/z 22), but a considerably smaller response for Benzene (m/z 78) and slightly higher
response than the oilfield samples fro Acetic acids (m/z 60), respectively.

The Methane anomaly associated to a liquid hydrocarbon anomaly indicates the presence of oil or
condensates nearby; this is confirmed by the oil bearing fluid inclusions identified by thin section
petrography. The Alkylated Napthenes anomaly without an associated Methane anomaly might
indicate contamination, but its association to an Acetic acids anomaly confirms the nearby presence of
oil or condensate. The combination of a Methane anomaly and an Acetic acids anomaly is signalling
the presence of a nearby hydrocarbon accumulation. The dominance of Acetic acids response over the
Benzene response indicates the presence of a liquid hydrocarbon accumulation nearby.
The small CS2 and C6+ hydrocarbons response indicates that the hydrocarbons are not biodegraded.

Figure 2 Ungumayo-1X and neighbouring oilfield specific compound identification for Methane (m/z
15), Alkylated Napthenes (m/z 97), Benzene (m/z 78), Acetic acids (m/z 60) and CS2 plus C6+
hydrocarbons (m/z 76). The red bar identifies a methane anomaly. Th green bar identifies a liquid
hydrocarbons anomaly. The black bar identifies sub-anomalous hydrocarbon concentrations. The
blue bar identifies Acetic acid anomalies .Depth in meters.

Ungumayo-1X well mass spectra patterns interpretation

The Ungumayo1X samples display well defined gas/liquid hydrocarbons mass spectra patterns
(Figure 3), very similar to those of the samples from the neighbouring oilfield. The water soluble
hydrocarbons mass spectra patterns for the Ungumayo-1X samples are not as fully developed as those
of the neighbouring oilfield. The absence of an oil column in the logs and the scarcity of oil bearing
fluid inclusions identified by thin section petrography indicate that this zone is a carrier bed for oil
migration. The presence of water soluble hydrocarbon enriched mass spectra indicates that it is an
active carrier either overlies a deeper oil accumulation or is located along the same reservoir that
contains the hydrocarbon accumulation.

72nd EAGE Conference & Exhibition incorporating SPE EUROPEC 2010

Barcelona, Spain, 14 - 17 June 2010
Figure 3 Ungumayo-1X petrophysic evaluation and Ungumayo-1X and neighbouring oilfield mass
spectra plot .Gas hydrocarbons enriched mass spectra painted pink. Liquid hydrocarbons enriched
mass spectra painted green. Water soluble hydrocarbons enriched mass spectra highlighted with a
dark green frame. Sulphur compounds enriched mass spectra highlighted with an orange frame. Non
hydrocarbons compounds mass spectra highlighted with a blue dotted frame. Sample location marked
by a green circle. Depth in meters.

Conclusions

The fluid inclusion volatiles mass spectrometry analysis for the Ungumayo-1X well Cenomanian
sandstone indicate the presence of a non biodegraded oil, associated to an Acetic acid anomaly,
indicating close proximity to a hydrocarbon accumulation updip, along the same sandstone, or in the
underlying reservoir.

The Ungumayo-1X well gas and liquid hydrocarbon enriched mass spectra patterns are similar to
those of the neighbouring oilfield samples, suggesting a similar oil compositions.

Acknowledgements

My acknowledgements to Cepsa Peru, for its authorization to submit this paper.

References

Aleman, A., Marksteiner, R. and Valasek, D. [1999] Petroleum systems along the northern Marañon Foreland Basin and
relationship to the Oriente and Putumayo Basins, Northern South America. In: Machare, j., Benavides, V. and Rosas, S.
(Eds.) 75 Aniversario Sociedad Geologica del Peru- Volumen Jubilar N°5. Sociedad Geologica del Peru, Lima, 27-43.

72nd EAGE Conference & Exhibition incorporating SPE EUROPEC 2010

Barcelona, Spain, 14 - 17 June 2010