URTeC: 1922938

Advanced Core Analysis Methodologies Quantify and Characterize

Prolific Liquid Hydrocarbon Quantities in the Vaca Muerta Shale
R. D. Williams*, D. M. Willberg, D. Handwerger, D. Ekart, J. Petriello, R. Suarez-
Rivera1, Schlumberger.
1. Author now with W. D. Von Gonten Laboratories

Copyright 2014, Unconventional Resources Technology Conference (URTeC) DOI 10.15530/urtec-2014-1922938

This paper was prepared for presentation at the Unconventional Resources Technology Conference held in Denver, Colorado, USA, 25-27 August 2014.

The URTeC Technical Program Committee accepted this presentation on the basis of information contained in an abstract submitted by the author(s) . The contents of this paper
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Abstract

The analysis of self-sourcing liquid-rich mudstones is complicated by the inherent heterogeneity of these ultralow-
permeability formations. Determining reservoir and completion quality requires a detailed understanding of how
rock properties, fluid saturations, hydrocarbon composition, and fluid thermodynamic properties are distributed
throughout the reservoir. In many cases, the rock and fluid properties are intrinsically coupled from both geological
and physical chemical perspectives and must be analyzed together. A wireline log–based heterogeneous rock
analysis (HRA), coupled with advanced laboratory analyses, was used to characterize the distribution of
petrophysical properties along a core spanning the entire section of the Neuquén basin Vaca Muerta shale. A novel
quantitative extraction and gas chromatography method was used to measure the total hydrocarbon composition
(C1–C30+) at multiple depths throughout the reservoir. The results of this combined rock-fluid study show that the
formation contains two distinct reservoir zones connected by a transitional zone. Each of these reservoir sections
owes their uniqueness to a change in depositional and diagenetic processes. This leads to local heterogeneity in
properties such as mineralogy, transformation ratio, and hydrocarbon composition, which could not be explained by
thermal maturity alone. A high degree of correlation was found between the rock and fluids in each of the reservoir
zones. Advanced core analysis studies of the Vaca Muerta shale found that the lower zone contains high quantities
of liquid hydrocarbons (~45g/kg of rock), but it has the lowest gas-to-oil ratio (GOR) and the highest viscosity and
also contains numerous ash beds that may reduce the overall completion quality of the section. The upper zone lacks
the overall liquid hydrocarbon volume of the lower (~10g/kg of rock), but it has a higher GOR, lower viscosity, and
fewer ash beds—properties that are favorable to production. The transitional zone maintains the high liquid
hydrocarbon content of the lower zone (~30g/kg of rock) while maintaining moderate GORs and viscosities and
being free of ash beds. This transitional zone represents the highest analyzed reservoir quality section in the Vaca
Muerta shale when both rock and fluid properties are considered together. The HRA method can be used for data
propagation to other regions of the Vaca Muerta shale.

Introduction

The Vaca Muerta shale, located in the Neuquén basin in Argentina, is a late Jurassic to early Cretaceous organic-rich
mudstone with economically significant hydrocarbon accumulations. Numerous geological studies have been
completed in the Vaca Muerta, all highlighting the prolific quantities of hydrocarbons contained within this
reservoir. Studies have shown that the formation is the result of a multi-depositional sequence (Kietzmann et al.
2014) that has ideal conditions for preservation of organic material (Doyle, et al., 2005) and often contains bitumen
veins (Cobbold et al. 1999). These properties, along with field data showing good production from the formation
(Badessich and Berrios 2012), suggest that the Vaca Muerta shale could be a highly productive unconventional
reservoir.
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While the potential of the Vaca Muerta shale appears to be without question, a search of the existing literature shows
very little analysis of the rock properties and hydrocarbon fluid properties that drive production. Knowledge of key
reservoir quality indicators such as permeability, hydrocarbon filled porosity, and hydrocarbon fluid properties (e.g.,
GOR, viscosity, etc.) is essential for determining the true production potential of the reservoir. A series of advanced
core analysis methodologies are used in conjunction with a wireline log-based rock classification methodology to
characterize the distribution of key petrophysical properties along a core spanning the entire section of the Vaca
Muerta shale in the Neuquén basin. Furthermore, the combination of these properties and their potential impact on
production is assessed to determine sections of the reservoir with the best mixture of reservoir quality, liquid
hydrocarbon content and completion quality.

Workflow and Results

The study well in the Vaca Muerta shale was logged with a quad combo tool, and the gamma ray, resistivity,
density, p-wave velocity and neutron porosity logs were used to develop a log-based rock classification. Each of
these rock classes was defined via an unsupervised classification algorithm over the zone of interest using the multi-
dimensional set of log measurements. The logs chosen collectively respond to variations in texture and composition
of the rock and so a classification scheme based on these logs should, by the laws of material science, define zones
of similar or dissimilar material properties (Suarez-Rivera, et al. 2013). An additional benefit of building an initial
model using unsupervised classification is that the classes themselves will naturally partition in such a manner as to
uniquely cluster the variance space of the inputs. What this means in practice is that the classes will balance the
competing influences of class size and class uniqueness, such that the end result will have classes that satisfactorily
discriminate the variability of all the logs (and by extension their range of material properties), and are also uniquely
recognizable when used as training data for supervised classification in subsequent wells using the same log inputs.
In other words, this becomes a predictive tool such that once the classes are properly characterized through rock
testing, recognition of the classes in subsequent wells (presumably without core) will imply similar material
properties, per class, as in the model well. Thus, this becomes a powerful tool to map units of known properties
across the basin based on pattern recognition techniques.

The log data used to determine these rock classes are shown in Fig. 1, as are the rock classes themselves (indicated
with a colored block in Track 5). As these classifications are based solely on log data, they are initially undefined in
terms of rock properties. Representative core samples were taken from each of the classes, therefore, to characterize
the rock. Standard rock properties, including: saturations, porosity, permeability, total organic carbon (TOC) and
mineralogy were determined for each sample, and these data were used to identify the properties that led to the
differentiation in the log-based rock classification. For example, the brown and black rock classes in the lower
section of the Vaca Muerta shale (Fig. 1) have similar water and hydrocarbon saturations, but they are differentiated
on the basis of their differences in TOC and porosity. Similarly, a smaller subset of core measurements were taken
for advanced characterization methodologies, and these will be described in the following pages. In general, the logs
identified three separate zones in the Vaca Muerta shale core described hereafter. The uppermost zone consists of
primarily the light and dark blue rock classes—calcareous, calcareous/argillaceous mudstones with moderate
effective porosities (2 to 3% of bulk volume), moderate TOCs (1.5 to 2% by weight) and low pressure decay
permeabilities (~100 nD). An example of a core and thin section from the dark blue rock class - a calcareous
mudstone with abundant calcispheres and recrystallized fossils - is shown in Fig. 2A. The middle, transitional zone
is made up of the yellow and uppermost black rock classes—calcareous/argillaceous mudstones with high effective
porosities (6 to 8% of bulk volume), TOCs (5 to 8% by weight) and pressure decay permeabilities (130 to 175 nD).
An example of a core and thin section from the yellow rock class is shown in Fig. 2B. The lowermost zone of the
Vaca Muerta, which includes the zone commonly referred to as La Cocina, consists primarily of the brown rock
class—a calcareous/argillaceous mudstone with high effective porosity (~6.5% of bulk volume), TOC (4.25% by
weight) and pressure decay permeability (~160 nD). An example of a core and thin section from the black rock class
– a silty, argillaceous mudstone interspersed throughout the brown is shown in Fig. 2C. La Cocina itself, typically
marked by high gamma ray, is defined predominantly by olive and black rock classes, the difference being caused
by the influence of ash beds on the resistivity and bulk density logs (remember, the classes are defined by the
combination of all the logs as these each respond differently to the bulk material properties that influence texture
and composition). However, the ash beds exist beyond La Cocina and so influence the log signatures wherever they
appear. Outside La Cocina, these ash beds are typically denoted as purple and orange rock classes. An example of a
core and thin section of a reworked volcanic ash from the purple rock class is shown in Fig. 2D. The effect of these
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Fig. 1—Log measurements and associated rock classification of the cored interval of the Vaca Muerta shale. Track 1: formation names,
Track 2: gamma ray, Track 3: resistivity, Track 4: density, Track 5: HRA classifications. The Vaca Muerta shale section generally
consists of three zones: the upper light and dark blue rock classes, the yellow and uppermost black rock classes, and the lowermost mixed
brown/olive/orange rock classes. The Catriel sandstone underlies the lowermost zone of the Vaca Muerta.
URTeC 1922938 4

Fig. 2— HRA classification with associated core and thin section images. All thin section images were taken in plane-polarized light,
with a scale bar of 0.5 mm. Calcite is pink due to the application of Alizarin Red S. A) Calcareous mudstone with abundant calcispheres
and recrystallized fossils, representing the dark blue rock class from the upper Vaca Muerta section. The matrix is composed of micritic
calcite that is admixed with low quantities of clay minerals, resulting in a competent core interval (i.e., low fissility). Organic content is
low relative to samples from the transitional zone and the lower section. B) Calcareous/argillaceous mudstone from the transitional zone,
representing the yellow rock class. This sample is characterized by an elevated clay content and lower calcite content relative to samples
from the upper section. Calcispheres and nondescript, recrystallized fossil material are widely distributed. Organic content is elevated
relative to the upper section, resulting in the dark color of the matrix. C) Reworked volcanic ash, representing the purple rock class in
the transitional zone. Very high total clay content and clay expandability. Minor fossil material. In addition, silt-sized micas and
polycrystalline quartz are noted. D) Silty, argillaceous mudstone representing the black rock class in the lower section, with a distinct,
horizontal, calcite-filled vein. The maximum aperture of the vein is approximately 0.5 mm. Detrital quartz and feldspar grains are widely
distributed. The calcite content is low relative to the majority of samples in the transitional zone and upper section, and where identified,
calcite is in the form of veins or fossils. The matrix is largely composed of illite and illite/smectite clay minerals. Overall, the total clay
content and organic content are both considered high; the latter results in the dark color of the matrix.
URTeC 1922938 5

ash beds on the logs is so extreme due to drilling fluid imbibition and localized washouts that the surrounding rock
is often identified as a unique class. The red and olive rock classes are examples of this effect, and are always
observed above and below an ash bed. The red rock class always accompanies ash beds in the upper zone of the
Vaca Muerta, and the olive rock class always accompanies ash beds in the lowermost zone of the Vaca Muerta.
However, it should be pointed out that the ash beds, especially those that are quite thin, are not always recognizable
by logs in the Vaca Muerta. Their affect here is amplified by the coring process and the use of water-based muds.
Consequently, in logs less affected by the ashes (e.g. in wells drilled with oil-based muds), La Cocina would most
likely show up as a unique class unto itself. The Catriel sandstone underlies the Vaca Muerta shale as the green rock
class—a muddy sandstone with elevated effective porosity (~4.5% of bulk volume), low TOC (0.5% by weight) and
low pressure decay permeability (~90 nD).

To determine the quantity and composition of light hydrocarbons within the cored interval, a total of twenty-two 30-
cm-long canister desorption samples were taken from the six core runs that were successfully retrieved from the
Vaca Muerta shale over the course of 7 days. The samples were evenly spaced throughout the cored interval, since
logs had obviously not yet been collected for HRA, and each sample was cut from the core and sealed in a heated
vessel by a dedicated core preparation team so as to limit the amount of gas lost from the core once on surface. Once
in the preheated vessels (at mud circulating temperature), the volume of desorbed gas was measured and recorded.
This was continued in the field until the desorption rate was low enough to safely transport the core to the
laboratory. The amount of gas lost during core tripping was estimated from the early time desorbed gas volumes
according to the United States Bureau of Mines (USBM) method for determining total gas content (Diamond and
Levine 1981). The sum of the lost gas and desorbed gas for each sample is plotted in Fig. 3A in red. Select samples
of the desorbed gas were taken for compositional studies (C1 to C4+) throughout the desorption process, and the
percent methane of the total gas content is shown in Fig. 3A in blue. Interestingly, while there was no dramatic
change in the overall gas content throughout the cored interval, there was an abrupt change in the chemistry of the
gas that occurred between samples 11 and 12. The chemistry of the samples in the upper section of the formation
(Samples 1 to 11) had an average methane content of 72 mol%, while the samples of the lower section (Samples 12
to 21) had an average methane content of 42 mol%. Sample 22, being from the non-reservoir Catriel, had the lowest
gas content and could not be studied for composition due to insufficient volume. The composition was estimated
from Sample 21 because of the absence of data on Sample 22.

To determine the liquid hydrocarbon content and composition within the cored interval, a separate effort was
conducted with twenty-two 30-cm core samples collected adjacent to each canister desorption sample and
preserved on dry ice in a sealed container. The samples were maintained on dry ice during the entire coring job and
then shipped on dry ice to the laboratory, where they were prepared for hydrocarbon extractions. Each core sample
was slabbed for core description, and then the outer 1-cm of the core’s diameter was cut from the core to remove as
much of the mud contaminated surface as possible. All cutting operations were done with liquid nitrogen cooling to
avoid localized heating and losses of volatile hydrocarbons. Samples were only removed from their sealed vessels
during cutting operations. Each preserved core section was sub-sampled into three, 6-cm-long samples to determine
if there were local heterogeneities in the liquid hydrocarbon composition. These were typically located at the top,
middle, and bottom of each core sample. A small portion from each of the subsamples was crushed to powder in a
cryogenically chilled and sealed crushing cell, and this material was loaded into a solvent extraction cell for
extraction via a mixture of dichloromethane and internal standards at elevated pressure and temperature. This
methodology results in complete extraction of liquid hydrocarbons, and does so in a manner that uses very little
solvent. The low solvent content of the resulting extraction fluids (DCM + standards + C 5+ extracted hydrocarbons)
enables direct determination of the composition by C30+ gas chromatography (GC). More details on the extraction
methodology can be found in a similar study in the Duvernay shale (Davis et al. 2013).

The total extractable liquid hydrocarbon content is shown in Fig. 3B, and each sample is colored according the HRA
class it was taken from, as designated by the analysis of the log data from the well. The samples from the upper
section of the Vaca Muerta shale are primarily from the light blue and dark blue rock classes, with a few outliers in
purple and red. As mentioned earlier, these samples owe their different rock class designations to the presence of ash
beds in (purple) or near the preserved sample’s location (red). The total extractable liquid hydrocarbon masses in
this uppermost section of the reservoir average 10.9 g of oil per kilogram of rock. While they are far less than the
hydrocarbon masses contained in the lower section, they still remain within the range of numerous liquid producing
reservoirs currently under exploration and production (Davis et al. 2013, unpublished results). Samples from the
underlying transitional zone show a clear increase in total extractable liquid hydrocarbon content with depth
URTeC 1922938 6

(Samples 12 to 15), and have an average of 38.4 g/kg of rock. The lowermost section of the Vaca Muerta (Samples
16 to 21) have the highest extractable liquid hydrocarbon content, and average 44.2 g/kg of rock, with a peak at
Sample 17 (57.1 g/kg of rock). The Catriel sandstone—Sample 22—contains 6.5 g/kg of rock.

Interestingly, the trend of increasing extractable liquid hydrocarbons and variable transformation ratio (extracted
liquids/TOC) with depth does not appear to strongly correlate with the maturity of the rock (Fig. 4). Rock-Eval
pyrolysis data showed that the T max temperature remained relatively unchanged throughout Samples 1 to 17 (444.5
degC ± 1.9 degC), and then decreased at Sample 18 to a stable Tmax of 435.6 degC ± 3.2 degC throughout the rest of
the Vaca Muerta shale. However, vitrinite reflectance, another methodology used for assessing maturity, was
measured on a subset of the samples and indicated a consistent maturity throughout the Vaca Muerta (0.66 average
Ro). A potential reason for the change in transformation ratio and T max could be a change in the chemistry and
depositional environment of the Vaca Muerta shale—a point that will be discussed later.

Fig. 3—A) Total gas content (red) and percent methane (blue) of each core sample as determined via canister desorption and gas
chromatography. An abrupt change in gas composition can be seen at the transition from Sample 11 to Sample 12 where the methane
content of the gas dropped from 73 mol% to 43 mol%, respectively. B) Total extractable liquid hydrocarbon content of the core (grams
of oil per kilogram of rock) as determined by quantitative solvent extraction from cryogenically preserved core material and gas
chromatography. Each sample is shown with its corresponding HRA class color.

The total hydrocarbon content of the Vaca Muerta shale (C1-C30+) was determined by combining the data in Figs.
3A and 3B to determine the GOR of each sample. The mathematical recombination was generated with a
commercial pressure-volume-temperature (PVT) modeling program by modeling the density of the gas and bulk
liquid phases at standard temperature and pressure (STP) to determine the volumes of gas and oil contained in the
rock. This resulted in a measure of the GOR which was used to combine the gas and fluid chemistries into a single
hydrocarbon chemistry for the 60-cm section. This included gas data from canister desorption in a 30-cm section
and total extractable liquid data from the cryogenically preserved adjacent 30-cm sample. The recombination results
for each of the 22 samples (colored by their HRA class) are shown in Fig. 5A, which clearly shows the change in the
hydrocarbon chemistry that occurs between Samples 11 and 12. The upper section, aside from Samples 3 and 11,
had an average GOR of 91 vol/vol at STP (1 atm, 15.6 C). Samples 3 and 11 contained ash beds with very low oil
contents, so they had far higher GORs—943 and 285, respectively. It should be noted that these two values are the
result of sample heterogeneity across the 60 cm of core that was recombined for the GOR calculation. The gas
contents in the canister desorption samples were typical of the surrounding light blue rock and did not contain ash
beds, but the cryogenically preserved samples did. These ash beds had very low oil contents that resulted in a sharp
increase in GOR for the 60 cm section (i.e., normal gas content, low oil). The lower section of the Vaca Muerta had
an average GOR of 28 vol/vol and was bounded by the Catriel with a GOR of 43 vol/vol. These hydrocarbon
URTeC 1922938 7

recombinations resulted in predictions of the downhole fluid chemistry for each sample, as depicted in Fig. 5B.
Because the compositions of the extracted oils from the cryogenically preserved samples were very similar overall,
the compositions of the recombined fluids only differ substantially in the methane and ethane content due to the
GOR variation. The composition of both Samples 11 and 20 deviates from the norm due to the presence of ash beds
that contained very little liquid hydrocarbons. This resulted in the inability to detect some hydrocarbon isomers
directly via GC due to low signal intensity, but these isomers were detected gravimetrically and (mis)allocated as
C30+ components.

Fig. 4—Transformation ratio (blue) and Rock Eval Tmax (red) for the Vaca Muerta shale (1-21) and Catriel sandstone (22).

The mathematically recombined hydrocarbon compositions from each core sample were modeled as bulk fluids
using commercially available PVT modeling software to determine the fluid types and saturation pressures
throughout the Vaca Muerta shale (Fig. 6). With the exception of Sample 3, all samples are predicted to be black
oils at reservoir conditions. Sample 3, which had a skewed GOR due to the presence of ash beds, was predicted to be
in the gas phase at reservoir conditions (black star). This is highly unlikely for extractable oils that have such high
molecular weights (250+ g/mol). While the rest of the samples are all modeled as single phase black oils, they are
separated into two groups, primarily driven by their GORs. As such, samples from the upper section of the Vaca
Muerta have estimated saturation pressures within the range of 17 to 26 MPa, while the samples from the lower
section of the Vaca Muerta have estimated saturation pressures within the range of 3.7 to 6 MPa. A live sample was
not captured from this well for direct PVT measurements due to well productivity issues, so these saturation
pressures have not been calibrated, nor have the recombined fluid compositions been compared to produced fluids.
While these models have not been calibrated, they consistently predict two different hydrocarbon systems in the
Vaca Muerta shale with very different fluid properties.
URTeC 1922938 8

Fig. 5—A) Recombined GOR of each sample, as determined by canister desorption and quantitative solvent extraction from
cryogenically preserved core material. Each data point is colored to show its HRA class. As with the change in gas composition from Fig.
3A, there is an abrupt shift in sample properties that occurs between Samples 11 and 12. B) Recombined hydrocarbon composition
based on the GOR in Fig. 5A and the compositional data from Figs. 3A and 3B. Compositional differences are primarily confined to
methane and ethane content in the samples.

The distinction between the upper (predominantly light and dark blue classes) and lower sections (predominantly
brown class) of the Vaca Muerta shale is further shown in two additional datasets: the fossils in the core and the
biomarkers in the extracted hydrocarbons. As seen in Fig. 7, the presence (or absence) of 11 different fossils was
logged throughout the entire cored interval. Some fossils were identified throughout the Vaca Muerta, while others
were preferentially distributed in either the upper or lower sections. Ostracodes were almost exclusively located in
the upper section, while algal material, foraminifera, bivalves and brachiopods were almost exclusively located in
the lower section. Interestingly, the transitional zone between the upper and lower sections of the Vaca Muerta
(yellow/black rock classes) appears to have a higher proportion of charophyte spores and algal material. This section
also lacks the foraminifera that are concentrated in the lowest section (brown/olive). In general, more fossils were
found in the lower section of the Vaca Muerta than in the upper. These variations point to a change in the local
chemistry for each of these zones, which is also seen by evaluating the ratio of pristane to phytane in the
hydrocarbons (Fig. 8A). Pristane and phytane are two products of chlorophyll a breakdown, and their generation is
directly linked to the presence of oxygen (Peters et al., 2005). Fig. 8A shows that the ratio of these two components
decreases throughout the upper section and then sharply drops and stabilizes in the lower section, indicating
increasing anoxia. This anoxia trend with depth has been noted in previous studies (Doyle et al., 2005) and can
result in better preservation of organic material during deposition—an effect duly observed in the accompanying
TOC data. The trend towards anoxia is also accompanied by an increase in pyrite content, a mineral indicative of
sulfate reduction (i.e., anaerobic respiration) due to a low quantity of oxygen in the depositional system (Fig. 8B).
As anoxia affects the rock composition and texture, and hence the logs, it is not surprising that there is a correlation
with HRA classifications as well, as suggested by the capillary pressures in Fig. 6.
URTeC 1922938 9

Fig. 6—Predicted phase envelopes based on the recombined fluid chemistries in Fig. 4B, which are based on canister desorption data
and liquid hydrocarbon extraction data (color denotes HRA class). Aside from Sample 3 which had a GOR affected by the presence of an
ash bed, the upper and lower sections of the Vaca Muerta shale are both predicted to be single-phase black oils at reservoir conditions
(black star), albeit with very different saturation pressures in each section.

The measured data from each of the aforementioned analyses, representative of each of the rock classes, was used to
define rock-class by rock-class regression models relating the measured properties to the log responses. These
relationships were subsequently applied to the entire log, at the rock class rock class level, and combined to define
continuous profiles of each of the measured properties, along the length of the logged interval. These profiles were
then combined to develop a reservoir quality log, shown in Fig. 9, and all three zones of the Vaca Muerta shale are
identified. The logs that were used to define the rock classes (Track 5) are shown in Tracks 2 to 4, and are identical
to Fig. 1.

Track 6 shows the occurrence (dot) and thickness (length of line) of ash beds throughout the cored interval, and their
influence can be clearly seen by a sharp drop in the resistivity and bulk density logs. Ash beds are sparsely
distributed throughout the upper zone (light/dark blue), then almost non-existent in the transitional/middle zone
(yellow/black). While often very thin, their presence is noted numerous times throughout the lowermost zone of the
Vaca Muerta and influences the way La Cocina is recognized by the HRA due to their profound influence on bulk
density and resistivity. These beds could have a significant impact on fracture conductivity via clay swelling, and
should be avoided. Consequently, it is useful to preserve their recognition by keeping the bulk density and resistivity
logs in the HRA, so that in subsequent wells they can be flagged through the classification and dealt with
accordingly.

The presence of carbonate veins are shown in Track 7, and these too are non-uniformly distributed (see Fig. 2D).
The presence of these features could arrest fracture propagation via mechanical complexity, so dense populations of
these veins could act as pseudo containment—a potential containment boundary for fractures initiated in the
yellow/black transitional zone. Since thin carbonates are not so systematically different in their log signatures vs. the
shale proper, unlike the ash beds, they are not prominently identifiable through the logs. In other words, the effects
of thin carbonates on the inherently smoothed resolution of the logs are not so large as to exert undue influence on
log character, and hence HRA classes. What is apparent is that they are generally associated with the light blue,
URTeC 1922938 10

black and brown rock classes, and their occurrence is less prominent, or absent in the yellow, dark blue olive,
orange, purple red and green classes. This could be due to less favorable association to the major rock types of these
classes.

Tracks 8-12 describe the volumetrics of the rock and its associated pore space. It is clear from these traces that
porosity increases with depth, primarily due to the presence of increasing quantities of organic material. As these are
fundamental changes in rock texture and composition, they are also reflected in the HRA classes. The average
effective water saturation for the middle/transitional zone (6.5%) is substantially lower than the upper (17.3%) and
lowermost zones (14.0%) that bound it. Track 13 shows the transformation ratio of the hydrocarbon system as a
function of depth, with above average values being green curve fill and below average values being yellow curve fill
(not to be confused with the log-defined HRA classes of similar color). This trace should track with maturity, yet we
showed this remained unchanged throughout the interval. Instead, it appears to be highly variable. One region of
note is the transformation ratio of the middle/transitional zone which remains low, while a section right above the
middle/transitional zone (three light blue rock classes immediately above) is high. The gas chemistry suggests a lack
of mixing between these two sections at the current time, but the high transformation ratio in this upper section may
indicate that some fluids from the transitional zone have migrated and been trapped in this lowermost section of the
upper Vaca Muerta. Track 14 shows the predicted viscosity of the live fluid, and a clear increase in viscosity can be
seen at the interface between the upper and transitional zones. This property will clearly affect fluid mobility, so all
things being equal, fractures in the lowermost zone are likely to be less productive than those that are higher in the
reservoir. Considering the viscosity and the hydrocarbon volumes in the reservoir, the transitional zone maintains
the best balance of hydrocarbon filled porosity and viscosity. Track 15 shows the GOR of the hydrocarbons, which
has an inverse relationship with viscosity, as would be expected. The final Track, 16, shows the permeability of the
core samples to gas. The average permeability of the three zones are 110 nD, 160 nD and 140 nD for the upper,
middle and lower, respectively. The higher permeability of the middle/transitional zone again points to it as being
the best target for production, especially when considering that there appears to be a sweet-spot in the uppermost
portion of the transitional zone that has an average permeability of 190 nD.

As seen in the data presented, there appear to be two chemically distinct zones within the Vaca Muerta shale. These
zones encompass the upper and lower sections, with their segregation occurring at the interface between the blue
rock classes of the upper section and the yellow rock class of the lower. This interface effectively segregates the gas
chemistry, the GOR, and the estimated saturation pressures. It is also at this interface where effective porosity,
hydrocarbon-filled porosity and permeability increase for the lower section. As stated earlier, the upper section
appears to be a good reservoir because it contains similar quantities of liquid hydrocarbons to other unconventional
reservoirs in North America. Furthermore, the fluids in this section have the highest GOR and lowest estimated
viscosity of the cored interval—properties that could be of significant importance for production, even though the
hydrocarbon filled porosity and permeability are both less than the lowermost shale section. As to whether the
positives outweigh the negatives, one should further analyze the geomechanical properties of this section to see if
they are favorable for completion. This lowermost section contains prolific hydrocarbon quantities and high
permeability; however, these hydrocarbons have lower GORs and higher viscosities that could limit fluid mobility.
This section also contains complex mechanical stratigraphy that could arrest fracture growth, as well as pervasive
ash beds that could render hydraulic fractures ineffective via clay swelling. Fortunately, the middle/transitional
section (yellow and black HRA classes) retains the benefits of the lowermost zone (high permeability and high
hydrocarbon filled porosity), while avoiding some of the negatives (less complex stratigraphy and a moderate
estimated viscosity). Furthermore, geomechanical data suggest that the regional compressional tectonics would
concentrate local stresses in the upper zone and lower Catriel, providing good fracture containment. This transitional
zone has also been independently identified in the logs by Ejofodomi et al. (2013), who suggested different
completion parameters than the zones above and below. This transitional zone appears to have the best mix of
reservoir quality and completion quality parameters in this section of the Vaca Muerta shale, and thus appears to be
the best target for production.
URTeC 1922938 11

Fig. 7—A) Fossil log of the entire cored interval of the Vaca Muerta shale, with a red dashed line showing the transition from the
chemically determined upper and lower sections of the shale. Ostracodes are more prevalent in the upper section of the Vaca Muerta,
while the lower section is rich in algal material, foraminifera, bivalves and brachiopods. Other fossils like charophyte spores and
calcispheres are present in both sections, though they are not distributed equally.

Fig. 8—A) The average pristane to phytane ratio of the hydrocarbons found in the cryogenically preserved Vaca Muerta core samples
(determined via GC) versus the TOC. The decreasing ratio of pristane to phytane indicates a higher level of anoxia in Samples 12 to 22,
leading to better preservation of organic material. B) The average pristane to phytane ratio of the hydrocarbons versus pyrite content.
Pyrite is often an indicator of anaerobic respiration, which correlates with the predicted anoxia from the low pristane to phytane ratio.
URTeC 1922938 12

Fig. 9—Reservoir quality log of the cored interval of the Vaca Muerta shale. Each zone is idenfied in Track 1, and red or black dots in
each track represent direct core measurements. Track 1: formation names, Track 2: gamma ray, Track 3: resistivity, Track 4: density,
Track 5: HRA classifications, Track 6: ash bed log, Track 7: carbonate vein log, Track 8: rock volumetrics, Track 9: non-mineral
volumetrics, Track 10: water-filled pore volume, Track 11: porosity, Track 12: hydrocarbon-filled porosity, Track 13: transformation
ratio (extracted hydrocarbons/TOC), Track 14: predicted live oil viscosity, Track 15: GOR, Track 16: permeability.
URTeC 1922938 13

Conclusions

A series of advanced core measurements have been utilized to characterize the Vaca Muerta shale in the Neuquén
Basin of Argentina. These measurements have shown that the cored interval studied in this project contains three
distinct zones. An unsupervised classification of the multivariate log data for this well shows this, but further shows
additional subzones within each of the three major zones. These zones owe their uniqueness to a combination of
factors, such as their mineralogy, their starting organic material, their hydrocarbon composition, and their
petrophysical characteristics, all of which cause changes in the texture and composition of the rock that affect the
log responses.

The upper zone of the Vaca Muerta shale is a calcareous mudstone that contains economically significant quantities
of single phase liquid hydrocarbons downhole. The logs isolate these as dominantly two subclasses – light blue and
dark blue. The hydrocarbons contained in this zone have the highest GORs, the highest saturation pressures, and a
slightly different composition than the other zones within the Vaca Muerta. However, the zone has the lowest
permeability, lacks any obvious upward containment, and has problematic ash beds scattered throughout. The
middle/transitional zone of the Vaca Muerta shale is a calcareous mudstone that underlies the upper zone, and is
dominated by yellow and black rock classes identified by the logs. It has the highest permeability and contains 200%
more hydrocarbons than the upper zone, but it has a lower GOR and slightly higher predicted viscosity than the
upper zone. It has the fewest ash beds of each of the three zones and appears to have upper containment, which
makes it one of the best targets for hydraulic fracturing in terms of completion quality. Consequently, the
multidimensional log signatures that define the yellow and black rock classes suggest a “fingerprint” that can be
used to identify this section in other wells. The lowermost zone, dominantly brown, olive and some black rock class
is an argillaceous mudstone transitioning to a dolomitic mudstone that underlies the upper and transitional zones of
the Vaca Muerta, and overlies the Catriel sandstone (green rock class). This zone contains the highest quantities of
liquid hydrocarbons within the cored interval, and it has a moderate permeability. However, it has the lowest GOR,
the highest predicted viscosity and the highest occurrence of problematic ash beds.

The combined data from the advanced core analyses in this paper indicates that the best target for production in the
Vaca Muerta shale is the transitional zone between the upper and lower sections (black and yellow HRA classes).
This zone contains prolific quantities of liquid hydrocarbons in a high permeability matrix, with very few
completion quality concerns. The upper zone, having hydrocarbon quantities similar to other productive liquids-rich
unconventionals, is an appealing secondary target for production. Through the integration of these data to the logs
via the HRA classes, this section can be identified by proxy through correlation of the logs in subsequent wells to
this model.

Acknowledgements

The authors would like to thank Carlos Almeida, Guillermo Giordano, Matthew Lamb, Dustin Mortensen, Horacio
Narambuena, Sergio Ollarce, and Gabriela Prete for their valuable assistance in field operations. We would also like
to thank the technical personnel at TerraTek for collecting and interpreting core analysis results for this project.

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