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Compositional changes in crude oils from the Ayoluengo oil field and the
Hontomín well (Burgos, northwestern Spain)

Conference Paper · November 2012

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Compositional changes in crude oils from the Ayoluengo oil field and the Hontomín
well (Burgos, northwestern Spain)
A. PERMANYER (University of Barcelona), G. MÁRQUEZ (University of Huelva), J.L. GALLEGO (University of Oviedo)
Copyright 2012. ALAGO.

This paper was selected for presentation by an ALAGO Technical Committee following review of information contained in an abstract submitted by the author(s).

Abstract
This work aims to establish and compare the geochemical composition of both Ayoluengo and Hontomín oils (Burgos province,
northwestern Spain). Oils come from 12 wells from Ayoluengo field and from the Hontomin-2 well (HON-2). Liquid and gas
chromatography, gas chromatography-mass spectrometry and carbon isotopic determinations were used. Results denote that the
Ayoluengo oils have a notably similar composition. The HON-2 oil displays a saturated hydrocarbon percentage (60%) higher than the
Ayoluengo samples. Moreover, the n-alkane distributions for the Ayoluengo oils are very similar and characteristics of marine organic
matter: unimodal from n-C 13 to n-C 33 , with maximum peaks from n-C 15 to n-C 17. Additionally, the HON-2 oil shows a GC profile with
unresolved humps and a partial absence of n-alkanes between n-C 10 and n-C 20 , suggesting a biodegradation level equal to 2 according
to the Peters and Moldowan scale. Although other possible biodegradation mechanisms cannot be dismissed, the most plausible
explanation is that aerobic cultures and sulfate reducers may have entered the reservoir in injected fluids during drilling operations. The
pristane to phytane ratios above one suggest an organic matter deposited in a shallow marine environment under reducing conditions.
No significant variations in the different fragmentograms were observed in all analyzed samples. The high proportion of diasteranes and
the low C 28 steranes indicate, respectively, oil derived from clayey source rocks and very probably Late Jurassic or older in age.
Maturity parameters are typical of mature oils. Moreover, the Hontomín-2 crude displays a higher calculated vitrinite reflectance value
(approximately 0.86%) compared to the other samples. Finally, the much closed δ13C signatures (whole oil, saturates, aromatics,
asphalthenes and resins) confirms that all the studied oils were derived from the same source rock. These isotopic values are in
agreement with those of the Pliensbachian organic matter and demonstrated good oil-oil and oil-source rock correlations.

Key words: Ayoluengo oil field; Hontomín well; mature oils; biodegradation; biomarkers.

Introduction westward tectonic extension of the Pyrenees (Quesada et al.,

1997; Beroiz and Permanyer, 2011).
The Ayoluengo and Hontomín oil fields are located in
the Sedano basin, on the southwestern margin of the Basque- The Hontomín field is associated with a unique
Cantabrian Basin (Spain), Burgos province (see Figure 1). The middle Jurassic fractured carbonate reservoir, at a depth of
Ayoluengo field was discovered in 1964 (Merten, 2006). After about 1900 m. The Ayoluengo hydrocarbons are reservoired in
the discovery well (AYO-1) and between 1965 and 1990 more multi-layer sandy bodies from Purbeckian facies, at depths
than 50 wells were drilled. However, in 2011 only 12 wells are between 800 and 1500 m (Sanz, 1967; Alvarez de Buergo and
still producing. In addition, several non-commercial oil García, 1996). Interbedded sandy and clay levels are
discoveries have also been reported in the same area, responsible for the vertical discontinuity of the reservoir.
particularly the Hontomín field (1965). In 1968, Hontomín-2
(HON-2) exploration well was drilled (Beroiz and Permanyer,
2011). This well was re-opened in 1990 and then was
abandoned because water production was higher than 85%.
Recently, in 2010, the HON-2 well was once more re-opened.

This work aims to establish and compare the

geochemical composition of both Ayoluengo and Hontomín
oils (Burgos province, northwestern Spain).

Geological setting

The Mesosoic-Early Cenozoic Basque-Cantabrian

Basin (Fig. 1) has been folded and thrusted during the
Paleogene-Early Neogene Pyrenean orogeny. It consists of a Figure 1: Sketch map of the southwestern margin of the Basque-
north and south verging thrust belt that constitutes the present Cantabrian Basin (modified from Beroiz and Permanyer, 2011).
 -2-

Samples and methods

The studied oils were sampled from twelve wells in
the Ayoluengo oilfield, and one additional sample was
obtained from the Hontomin-2 well. An aliquot of each
sample was fractioned into saturated and aromatic
hydrocarbons, resins and asphaltenes compounds. Then,
maltenes were fractionated into saturated, aromatic, and resin
fractions by liquid chromatography (De la Cruz et al., 1997).
Saturated and aromatic hydrocarbons were analyzed
by gas chromatography-mass spectrometry (GC/MS). The
GC-MS analysis was performed on a 7890A GC System
(Agilent Technologies) coupled to a 5975C Inert XL MSD
with Triple-Axis Detector (Agilent Technologies).
Carbon isotopic determination on whole oil and
SARA fractions was performed using a Thermo Finnigan
1112 elemental analyzer coupled to a a Finnigan Mat Delta C
mass spectrometer.
Results and discussion
The n-alkane distributions for all the Ayoluengo oils
are very similar and characteristic of marine organic matter
(Peters et al., 2005): unimodal from n-C 13 to n-C 33 , with
maximum peaks from n-C 15 to n-C 17 , and no dominance of
odd over even n-alkanes was observed in the whole oil gas
chromatograms. The pristane to phytane ratio (Pr/Ph) averages
at 1.37 (Table 1), in agreement with an organic matter
deposited in a shallow marine environment under moderately
reducing conditions (Peters et al., 2005). The Pr/n-C 17 and
Ph/n-C 18 ratios (Table 1) revealed that all the crude oils under
study were generated from mature type II kerogen (Figure 2).
The Hontomin-2 oil shows a GC profile with an unresolved
hump, an unaltered isoprenoid fraction and a partial loss of n-
alkanes between C 10 and C 20 , suggesting a biodegradation
level equal to 2 according to the Peters and Moldowan scale
(Peters et al., 2005). Although other possible biodegradation
mechanisms cannot be dismissed, the most plausible
explanation is that aerobic cultures and sulfate reducers may
have entered the reservoir in injected fluids during drilling
operations.

Table 1 shows the bulk and sulfur composition of all

oil samples from the Ayoluengo oilfield and the Hontomín-2
well. Group type analyses (SARA fractions expressed as
weight percentage) indicate that the Ayoluengo oils have a
notably similar composition. The Hontomin-2 crude oil
displays a saturated hydrocarbon percentage (60%) higher
than the Ayoluengo oils, while the opposite applies to the
polar fraction (∼8%), and about a 32% aromatic hydrocarbon.
The measured API gravity varies from 26 to 37º (32º for
Hontomín-2 oil). These values are typical of mature oils
(Hunt, 1996).

Table 1: Bulk composition and generalized geochemical

properties of the Ayoluengo and Hontomín oil samples.
Ph/n-
Well Pr/Ph Pr/n-C 17 S ºAPI
C 18
Ayo-04 1.17 0.48 0.44 0.20 31.1
Ayo-05 1.24 0.50 0.44 0.18 34.7
Ayo-19 1.21 0.48 0.42 0.15 37.0 Figure 2: Whole oil gas chromatograms of the Ayoluengo and
Ayo-20 1.16 0.49 0.46 0.14 37.3
Hontomín oils.
Ayo-32 1.14 0.48 0.45 0.22 26.6
Ayo-35 1.10 0.47 0.46 0.20 32.5
Ayo-36 1.17 0.48 0.45 0.29 32.1 The common δ13C signature of all analyzed samples
Ayo-37 1.18 0.49 0.45 0.19 37.9 (whole oil, saturates, aromatics, asphalthenes and resins; Table
Ayo-38 1.19 0.49 0.44 0.18 29.6 2) suggests that the crude oils in the Sedano sub-basin were
Ayo-40 1.20 0.48 0.43 0.14 37.5
derived from the same source rock. These similar isotopic
Ayo-44 1.19 0.49 0.44 0.14 37.2
Ayo-46 1.22 0.51 0.45 0.23 35.8 compositions with standard deviation close enough to
Hon-02 1.47 5.39 2.65 0.30 32.0 analytical error (0.5 ‰) are in agreement with those of the
Pliensbachian organic matter (Jurassic marine sediments) and
 -3-

demonstrate a good correlation between oils and source rock These crude oils show similar calculated-equivalent vitrinite
sample from the Cordovilla outcrop. reflectance values (average Rc 1 of 0.71%), which is indicative
of a thermal maturity level within the oil window. However,
Table 2: δ13C values (‰) in whole oil and SARA Hontomín-2 crude oil displays higher %20S and %ββ values
fractions for the Ayoluengo and Hontomín samples. (∼50 and 66%) in comparison with the Ayoluengo samples.
The latter value supports a maturation level (eq.Ro ≥0.8) close
Well OIL ASP SAT ARO RES
Ayo-04 -29.94 -28.95 -30.39 -29.44 -29.38
to the maximum peak oil generation (Hunt, 1996). Quesada et
Ayo-05 -30.08 -29.14 -30.38 -29.34 -28.97 al. (1997) reported lateral changes in source- rock maturity in
Ayo-19 -30.06 -29.21 -30.37 -29.45 -29.63 the studied area depending on burial histories during
Ayo-20 -30.13 -29.37 -30.52 -29.57 -29.48 Purbeckian-Wealden times, which would account for the two
Ayo-32 -29.99 -29.31 -30.11 -29.32 -29.51 different levels of maturation observed in the samples from the
Ayo-35 -29.80 -29.34 -30.32 -29.66 -29.56
Ayo-36 -30.10 -29.35 -30.72 -29.71 -29.70
Ayoluengo and Hontomín.
Ayo-37 -30.09 -29.04 -30.42 -29.57 -29.73
Ayo-38 -29.98 -28.96 -29.87 -29.12 -29.53 All crude oil samples show a common hopanoid
Ayo-40 -30.05 -28.73 -30.07 -29.24 -29.18 distribution pattern (177 and 191 m/z fragmentograms) (Figure
Ayo-44 -30.10 -28.86 -30.01 -29.58 -29.67 3). The series of 18α(H)-neohopanes (DTs, Ts, C 29 Ts, and
Ayo-46 -29.93 -28.90 -30.41 -30.12 -29.63
Hon-02 -29.56 -29.14 -29.40 -28.51 -28.59
tentatively C 30 Ts) appears to be clearly present,
Rock -29.55 -29.10 -30.15 -29.50 -29.25 suggesting rearrangement reactions related to clay
catalysis (Li et al., 2009). However, the formation of these
No significant variations in the m/z 217, 218 and 259 rearranged hopanes can not be always attributed to catalytic
fragmentograms were observed in all analyzed samples. We effects due to clay-rich source rocks (Michaelsen et al., 1995),
observed a dominance of the series of 13β(H),17α(H)- and 24-norgammacerane may coelute with C 30 Ts (Nytoft et
diacholestanes (20R and 20S) and, to a lesser extent, al., 2006). Also it can be noted that the Ayoluengo oils show
13α(H),17β(H)-diacholestanes (20R and 20S). Both series of lower ratios of tricyclopolyprenanes to hopanes compared to
rearranged steranes range from C 27 to C 29 and their relative Hontomín-2 oil, which is consistent with an eq.Ro value above
concentrations are C 27 ≈ C 29 > C 28 . The high proportion of 0.75% for the latter oil (van Graas, 1990).
diasteranes and the low C 28 steranes denote, respectively, oil
derived from clay-rich source rocks and very probably Late
Jurassic or older in age (van Kaam-Peters et al., 1998).

Table 3: Molecular parameters for the saturates and aromatics in

sampled oils from the Sedano sub-basin.
Well %22S %20S MPI-1 Rc 1 %ββ Rc 2 MDR
Ayo-04 59 44 0.44 0.71 59 0.68 3.24
Ayo-05 59 42 0.43 0.69 60 0.68 3.03
Ayo-19 59 44 0.47 0.71 60 0.71 3.48
Ayo-20 60 43 0.45 0.70 59 0.69 3.28
Ayo-32 58 44 0.50 0.74 59 0.72 3.23
Ayo-35 59 45 0.45 0.73 60 0.69 3.20
Ayo-36 59 44 0.43 0.72 59 0.68 3.07
Ayo-37 60 43 0.49 0.71 59 0.72 3.31
Ayo-38 59 44 0.46 0.72 58 0.70 3.11 Figure 3: The m/z 191 and m/z 177 ion fragmentograms showing
Ayo-40 58 43 0.47 0.71 58 0.71 3.37
terpane and norhopane distributions for a representative Ayoluengo
Ayo-44 59 44 0.47 0.72 59 0.71 3.25
oil sample (A and C), and the Hontomín oil (B and D).
Ayo-46 59 45 0.46 0.72 59 0.70 3.19
Hon-02 60 53 0.79 0.80 66 0.88 4.30
Notes: %Rc 1 =0.01·(33.33+0.487·%20S); % ββ=(R+S)C 29 αββ sterane ratio; As shown in the representative m/z 178+192
MPI-1=1.5·(2-MP+3-MP)/(P+1-MP+9-MP); %Rc 2 =0.4+0.6·MPI-1; MDR or fragmentograms for the Ayoluengo and Hontomín oils, the
methyldibenzothiophene ratio=4/1 isomers; %20S=5α,14α,17α(H)- distribution pattern for the methylphenanthrenes (2 < 3 < 9 >
stigmastane ratio, and %22S =17α,21β(H)-29-homohopane ratio.
1) corroborates that these crude oils were generated from a
Lastly, the percentage of 20S and ββ ratios in the marine source rock (Budzinski et al., 1995). In addition,
Ayoluengo oils average 44 and 60%, respectively (Table 3). methylphenanthrene indices (MPI-1; Radke and Welte, 1983)
 -4-
were calculated (Table 3), confirming that the Hontomín-2
crude displays a eq.Ro 2 equivalent to 0.86%, which is
consistent with the fact that MPI-1 only becomes a valid
maturity indicator for non-terrestrial organic matter at values
above 0.7 (Boreham et al., 1988). The
methyldibenzothiophene ratio (MDR; Radke, 1988) is a
universal indicator of maturation level at vitrinite reflectances
around 0.8 % and can be used to check those based on steranes
(Rc 1 ) and phenanthrenes (Rc 2 ).
Conclusions
1. Oils from the Ayoluengo field and the Hontomín-2 well
originate from the same Liassic siliciclastic source rocks
deposited in a marine environment under oxygen-depleted
conditions. The Hontomín-2 crude is more mature (near the
maximum oil peak generation) than all the Ayoluengo oils
(early oil window).
2. Ayoluengo oils have not been significantly biodegraded. On
the contrary, the Hontomín-2 oil presents evidence of being
affected by slight microbial degradation (PM level 2), thus its
API gravity has certainly been reduced, which is confirmed by
the average percentage of polar compounds. Biodegradation of
Hontomín oil was possibly caused by the injection of aerobic
and sulphate-reducing bacteria into the Hontomín reservoir
during drilling operations.
Acknowlegments
This study was found by the Spanish Government (Research
Project CGL2010-15887). Authors are grateful to Leni Gas &
Oil PLC for facilities to sampled oils in the Ayoluengo oilfield
and the Hontomín well.
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