SPE 159976

Reconciling Retort versus Dean Stark Measurements on Tight Shales

D.A. Handwerger, Schlumberger Innovation Center; D. Willberg, Schlumberger Innovation Center; M. Pagels,
Schlumberger Innovation Center; B. Rowland, Encana Oil and Gas and J.F. Keller, TerraTek, A Schlumberger
Co.

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, USA, 8-10 October 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of th e paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract

Due to the complexity of tight shale reservoirs, core analysis has become an increasingly important source of data for
evaluating these systems. However, as there are no generally agreed upon testing protocols, there are competing methods for
obtaining such primary data as fluid saturations and porosity. The two most commonly employed commercial methods are
Dean Stark toluene combined thermal and solvent extraction and thermal extraction by retort. However, the impact of these
protocols on the rock and its fluid phases is different, primarily due to the abundance of clays. While the Dean Stark
extraction produces a total porosity and total water saturation, data suggest significantly elevated values of these parameters
relative to what is measured through the retort process, resulting from significantly higher amounts of water recovered. This
distinction is fundamentally important for using core analyses in shale for calibrating logs and/or determining reserves, as
both methods claim to report the same parameters.

To understand this effect, we have assembled a data set of compatible core analyses from various laboratories from several
wells for a tight-gas shale reservoir in the United States. In addition, we conducted thermogravimetric analysis and Karl
Fischer Titration with methanol extraction on splits of the same samples. The retort, thermogravimetric, and Karl Fischer
data generally agree in the amount of water eluted from the samples (per gram of rock), while the Dean Stark data show
significantly more water. We suggest this excess water could be a portion of the structural water in the clays, which should
not contribute to porosity and saturation. Additionally, there is a relationship between this excess water and the total clay
content from XRD. This correlation to XRD analyses suggests that a correction can be determined, leading to more accurate
porosity and saturation values necessary for proper reserves estimations.

Introduction

The measurement of water saturations in unconventional rocks during core testing is complicated by the large variety of local
water environments existing in these complex heterogeneous rocks. The water in each of these local micro-environments –
the pores in the kerogen, pores in the mineral matrix, clay surfaces, gypsum nodules, opaline silica etc. – each have their own
associated chemical potentials. In a few reservoirs the most loosely held water – that which evolves at the lowest temperature
in the TGA – may actually be producable during production (as a liquid or condensate water). More tightly bound capillary
water requires a great deal of energy to liberate. This water will never be produced, but knowing its volume is important for
quantifying the hydrocarbon saturations and effective porosity of the rock. In most unconventional rocks, especially those
with a high argillaceous content, a certain fraction of the water is so tightly bound as part of the clay structure it should be
considered as part of the rock matrix, rather than a component of the saturating fluids existing in the pore nextwork.
However, this “water” has hydrogen, and so neutron porosity logs are sensitive to it. As a result, it can be helpful to quantify
how much there is, because accounting for it can make neutron logs more useful as a measure of “total” water and organic
content (e.g. Handwerger et al., 2011). Consequently, how one assigns the boundaries between the “types” of water is a
significant practical problem in unconventional core analysis.

A commercial laboratory system that successfully addresses these issues has to be reproducible, consistent and fast (to keep
up with commercial demands). A method that would measure the water characteristic function (Jury, et al., 1991; Coussy,
2 SPE 159976

2010) (the plot of the water’s chemical potential relative to a standard state as a function of Sw) would thoroughly
characterize the continuum of loosely to tightly bound water for each sample. This would be useful for some research
projects but could be overkill for routine work as the overload of detailed data may make analysis and decision making
unnecessarily complex. A more practical alternative is for the method to consistently specify and quantify the distribution of
water “types” between loosely bound and tightly bound environments.

Specifying the types of water, and the boundaries between them depends primarily on the particular test method used to
measure the water and to a lesser extent on the operator’s judgement. One can argue that the only unambiguous assignment
of water volume in the rock sample is the total water – which includes structural/hydroxyl water that is only released at high
temperatures not applicable to oil and gas operations. The continuum of potential energy states of water in unconventional
rocks is illustrated in the thermogravimetric (TGA) transient shown in figure 1 (Handwerger, et al., 2011). The two
transients show the water release profile for a Marcellus Shale sample. During a TGA experiment an as-received rock
sample is placed on a microbalance within a precision oven that is continuously flushed with dry nitrogen. The mass of the
sample is measured and recorded as a function of an applied temperature ramp. The sample in figure 1 shows a continuous –
but not constant – release of water with increasing temperature. The water from a particular micro-environment is released
only when the applied thermal energy exceeds the potential energy. What these transients in figure 1 highlight is that
different commercial laboratory measurements, operating under different temperature, pressure and solvation regimes will
most likely interrogate this continuum at different locations, and will measure different amounts of water. Therefore, the fact
that different methods of measuring saturations give different values is not a surprise but is an expected result.

In core analysis, two dominant methodologies are used by the various commercial labs for determining fluid saturations and
porosity: 1) the “GRI method” (e.g. Luffel and Guidry, 1989; Luffel and Guidry, 1992; Sondergeld, et al., 2010a), which is
basically a Dean Stark toluene solvent extraction (API Recommended Practice 40); and 2) the retort method (also described
in API Recommended Practice, for conventional rocks. Described for unconventional rocks in Handwerger et al., 2011),
which is fluid extraction through sequential heating of the sample under atmospheric pressure. It has been reported that the
two techniques produce different results for apparently similar rocks (e.g. Spears, et al., 2011). The most likely hypothesis to
account for this explanation is that the two methods sample (extract) water from the rock at different points along the
continuum of potential energy states. To this end, we have assembled a data set in a thermogenically mature shale gas play to
try and understand the nature of these differences.

The retort method, is performed by taking the sample (typically crushed material, though this is not required) and heating it in
air to extract the fluids (Handwerger, et al., 2011). As done commercially, the heating is done to three pre-defined
temperature steps. The first is the same temperature as the boiling point of toluene (110 °C) to extract the free pore fluids, the
second is 350 °C to extract the capillary/interlayer clay water, and the third is 700 °C, to extract the structural/hydroxyl water.
For an exhaustive discussion on retort analysis in shales, and the determination of petrophysical parameters as a result, please
refer to Handwerger, et al., 2011.

Figure 2 shows retort data (Handwerger, et al., 2011) from a commercially producing siliceous and a commercially producing
argillaceous mudstone, but at discrete 50 °F temperature steps, rather than the three strategic temperatures used commercially
(though using the same equipment) and measuring water volumes and masses recovered instead of sample mass loss. The
conclusions of that paper were that the lower temperature hump comprises the free pore water and capillary/interlayer clay-
bound water, and the upper temperature hump comprises the structural/hydroxyl water in the clay minerals themselves.
Chemically speaking, the lower temperature hump reflects the extraction of free water and water bound via weaker Van der
Waals forces, and the high temperature hump reflects the extraction of water bound via stronger covalent or ionic bonds
within the clays. Since Van der Waals bonds are of much lower energy than covalent/ionic bonds there is a large gap of
several hundred degrees F between these two major zones of released water.

The TGA experiment shown in figure 1 operates on an analogous physical principle as the retort method (however the mass
of the rock sample is recorded rather than the mass of the water extracted). As reported in Handwerger, et al., 2011, the mass
change and the derivate thereof (i.e., the instantaneous fluid release), show the same characteristic bimodal water-release
profile as the retort data. It is important to note however that the slope of the mass curve in figure 1 between 200 °C and
400 °C is not zero. Water continues to evolve, albeit at much lower rates.
SPE 159976 3

Figure 1: Thermogravimetric analysis (TGA) of a

Marcellus shale sample. The green line shows the loss
in mass (reported as weight (%) as a function of
temperature. The majority of this is water being
evaporated from the sample. The blue line is the
derivative of the mass curve showing the characteristic
“two humped” behavior. The lower temperature hump
represents free and loosely-bound capillary/interlayer
clay water, the higher temperature hump is the
structural/hydroxyl water. (From Handwerger, et al.,
2011)

The Dean Stark method, specifically as outlined by the Gas Research Institute (e.g., Luffel and Guidry, 1992) for shales,
involves bathing the rock sample in toluene at the vapor/liquid boiling point of 110 °C. This is done in an assumed closed
(though not evacuated) environment, where the toluene vapor extracts oil and water from the sample. The water is condensed
into a receiver vessel, and the toluene is continually refluxed through the sample, extracting more fluids. When the
production of water ceases and/or the reflux has proceeded for a fixed period of time, it is deemed that all the fluid has been
extracted and the sample is then oven dried to remove any residual toluene in the sample. The amount of water recovered is
compared to the amount of mass lost (accounting for the density of the water, which is typically 0.997 g/cc), and any
discrepancy is attributed to oil, which came from the rock but is non-recoverable because it is dissolved in the toluene. As
propsed by GRI (e.g. Luffel and Guidry, 1992), using whole core samples, this process can take a month or more, though
using crushed rock, is typically done in two weeks or less. The first week is the actual solvent extraction; the second week is
spent oven-drying the sample. After oven-drying, a He-porosimetry experiment is run to measure the total pore volume so
that saturations and porosity can be calculated. Additionally, a chloroform-methanol extraction can be done to remove salts
left behind by the distillation process to “clean out” the pores prior to the He-porosimetry experiment.

The Dean-Stark distillation for measuring water is fundamentally different from both the retort and the TGA methods in that
in addition to thermal energy the extraction is performed in the presence of an introduced wetting solvent. Although the
water molecules are eventually spatially seperated from the sample by diffusion in the vapor phase – during the distillation
process the rock is exposed to both toluene vapor and liquid in the thimble of the Dean Stark apparatus at the nominal boiling
point of 110 °C. As discussed below, and in accord with much solution chemistry, it is a reasonable hypothesis that the
presence of the solvent facilitates the breaking of inter-molecular bonds (both hydrogen bonds and van der Waals) between
the adsorbed water molecules and the various surfaces in the rock. At the molecular level the processes of striping water
molecules off the surface will be complex, and will vary from location to location. The energetics and rates of the reaction at
the local level will be highly variable due to heterogeneity in the rock composition, the surface chemistries, the local
concentration of salts, the local electrostatic, field and the local dimensions of the pore. However, we expect that the
presence of the liquid solvent facilitates the water extraction from the variety of capillaries and surfaces of the rock in at least
two ways. First, due to its lower surface tension than water (28.4 mN/m versus 72.8 mNm at 20.0 °C) liquid toluene can wet
the rock surfaces being exposed by the removal of the water – thereby lowering the overall chemical potential of the process.
Furthermore, water has a small but significant solubility in toluene (Nguyen-Huynh, 2011). Refluxing the sample for many
days over a large excess of toluene, and continuously stripping out the water can therefore be a slow, but efficient and
continuous method of water removal. It has been noted often in the conventional core literature that Dean-Stark extractions
are prone to causing excessive desiccation of clays in shalely sandstones. The net effect of the solvent is to accelerate the
release of hydrous phases from the rock and blur the distinction between weakly bound clay water and more strongly bound
clay water.
4 SPE 159976

Figure 2: High-resolution retort of a siliceous shale sample and an argillaceous shale sample. Note the similarity in behavior
between the two samples, and in comparison to the TGA results in figure 1. (From Handwerger, et al., 2011)

The Data

We collected 28 samples from several different cores all taken in the same thermogenically mature US gas shale. Splits of
each sample were sent to a commercial lab running the Dean Stark method and splits were run using retort, also under
commercial protocols. The samples were taken as biscuits out of the core, and each biscuit was subdivided into two adjacent
horizontal pieces to eliminate any chance that the pieces were different due to vertical heterogeneities in the rock. One piece
was run using the retort protocols of the Tight Rock Analysis (TRA) method outlined in Handwerger et al., 2011 (this is the
only commercially available retort method), and the other piece was run using the GRI protocol. XRD data were also
collected on the retort samples. Figure 3 shows a comparison of the sample bulk densities reported with the retort data and
the GRI data by the labs that conducted the experiments. Since they are substantively similar, the starting point for all
porosity and saturation calculations is essentially the same, eliminating this basic step as the start of a potentially cascading
set of errors.

2.75 One fundamental difference between retort and Dean Stark

Retort sample bulk density (g/cc)

methods is in the number and types of fluids evolved from the

2.7 samples that can be discriminated, and how they contribute to
2.65 porosities and saturations. In the Dean Stark method, only one
measurement of water is made for the sample – meant to be an
2.6 aggregate of free and loosely bound (capillary/interlayer) clay
2.55 water. This leads to reported “total” porosities and saturations
only. In retort, multiple water measurements are made as a
2.5 function of increasing temperature, such that a laboratory
procedure can be designed to independently measure effective
2.45 porosity and free pore water saturation, “total” porosity and
2.4 y = 1.003x saturations (again, the aggregate of free and capillary/interlayer
R² = 0.9345 clay-bound water, as explained above), and an additional phase
2.35 of structural/hydroxyl clay water. The free and loosely-bound
2.3 2.4 2.5 2.6 2.7 2.8 clay water (called the capillary/interlayer water above, and in
DS sample bulk density (g/cc) Handwerger, et al., 2011) combined make up the first hump of
water release in retort (Figures 1&2), while the
structural/hydroxyl water is attributed to the higher-temperature
Figure 3: Comparison of the bulk densities of the samples
run using retort and those run using the GRI protocol. second hump (e.g. Pallatt and Thornley, 1990). While the water
Each sample’s bulk density was measured by the laboratory release is a continuum, the clear discrimination of two humps of
that conducted the experiment, and was not measured by water relase that account for the vast majority of all water
the sampling lab prior to sample distribution. extracted suggests that at least the combined water contributed
by the first hump is consistent within the retort process.
Supporting this, Handwerger, et al, 2011 showed that for several different types of commercially producing shale reservoirs
(Barnett, Marcellus, and Haynesville), the basics of this water release profile are the same, and only becomes muddied with
the introduction of a significant amount of smectite (e.g. the Wilrich). If the first hump is indeed the total of free and loosely-
bound clay water, then it should be the common datum between the two methods from which the total porosities and total
water saturations are determined. As a result, comparisons made between the two data sets in this paper are made at this
SPE 159976 5

point. More specifically, total porosity and total water saturation are measured at the second retort temperature (350 ˚C)
(Handwerger, et al., 2011), and the amount of water evolved there is compared to the amount of water that comes out of the
GRI experiments, as are the saturations and porosities that result.

The comparison data show that the Dean Stark method total water saturations and the total porosities are systematically
higher than the retort total water saturations and total porosities (Figure 4). However, the porosity is not higher than what
would be deduced if one added in the structural/hydroxyl water (Figure 4a). Adding in the water volumes associated with
hydroxyl/structural water extraction at significantly elevated temperatures is purely an academic exercise of carrying through
the math typically employed in calculating saturations and porosities, just with an additional amount of water. No He-
porosimetry experiments were conducted post-retort, nor would such experiments be valid because of mineral changes likely
to occur in the rocks at such high temperatures. The resulting “all porosity” and “all saturation” are, again, a purely
mathematical exercise to illuminate how much water could be recoverable from the system. Regardless, what this suggests is
that while the GRI method is recovering excess amounts of water relative to total porosity and total water saturation as
measured using retort, it is not more water than is available in the system when one considers the water recovered in retort as
the second hump (the structural/hydroxyl water). This suggests that any excess Dean Stark water could be intrinsic, though it
does not eliminate the possibility of external contamination.

A Comparison of GRI porosity and TRA porosities B 12

18 10
16 Retort Total Porosity
14 8
12
Porosity (%)

10 TRA Effective Porosity 6

8 TRA Total Porosity
4
6 GRI porosity
4 2 y = 0.7631x
TRA "All Porosity"
2 R² = 0.8487
0 0
0 5 10 15 20 25 30 0 5 10 15
Sample Number DS Porosity

C Comparison of GRI and TRA water saturations D 70

Retort Total Water Saturation

70 60

60 50
H2O Saturation (%)

50
40
40
GRI H2O sat 30 y = 0.5951x
30 R² = 0.3006
TRA Effective H2O Sat 20
20
TRA Total H2O Sat
10 10

0 0
0 5 10 15 20 25 30 0 20 40 60
Sample Number DS Water Saturation

Figure 4: Comparison of GRI/Dean Stark porosity (a & b) and water saturation with retort porosities and water saturations (c &
d). Note that Dean Stark water saturations are systematically higher than retort total water saturation, and Dean Stark porosity
lies in between retort total porosity and what the porosity would be if one (wrongly) included the structural/hydroxyl water as
porosity also. Also note that the slopes of the best-fit lines in b & d show that the Dean Stark porosity and water saturation are
systematically higher than the retort total porosity and total water saturation.

Figures 1 & 2 and Handwerger, et al., 2011 demonstrate that the water release profile under retort conditions is very well
controlled, and very consistent. Water volumes, and therefore porosities and saturations, are not inferred but are directly
observed, and are measured at consistent, well-defined locations in the water-release continuum that separate the water bound
by weaker forces (e.g. Van der Waals forces , and capillary/interlayer water) and stronger forces (e.g. ionic/covalent bonds
the binds the structural/hydroxyl water). What is in question is the excess water recovered through the Dean Stark method
relative to retort at what should be the common datum. Figure 5 shows the differences in the actual amount of water
recovered, per gram of sample, between the Dean Stark method and the retort method at the various retort temperatures.
Again, we see an excess in the amount of water recovered through the Dean Stark method, and this time not normalized by
additional parameters such as pore volume or bulk volume that give us total saturation and total porosity, as in figure 4. This
shows further evidence that the Dean Stark method actually recovers more water and that the discrepancy is not purely in the
measurement of the rock bulk volume or grain/pore volume.
6 SPE 159976

0.025 retort water per gram (cc/g)

This is worth considering, because in the
Recovered water (cc/g)

0.02 DS water per gram (cc/g) retort method He-porosimetry is conducted

prior to fluid extraction, on as-received
0.015 sample, and the resulting pore volume is
0.01 reported as the “gas-filled porosity”. In the
GRI method He-porosimetry is conducted
0.005
after Dean Stark, and the resulting pore
0 volume is reported as the “total porosity”.
0 5 10 15 20 25 30 This means that total saturation and total
Sample number porosity are forward calculated in the retort
method by adding the amount of water
Figure 5: Comparison of extracted water volumes for each sample, normalized to recovered at each step (and associated
the size of the sample. volume increase, accounting for
appropriate fluid densities) to a foundation
of the gas pore volume, while in the GRI method, the total saturation and total porosity are back calculated by comparing the
amount of water recovered to the pore volume measured after the fluids have been extracted (see appendix). This introduces
its own set of uncertainties, because if the He-porosimetry is conducted post-Dean Stark, but in the absence of a chloroform-
methanol extraction, then the resulting pore volumes could be too small because of residual salts left in the pores from the
Dean Stark distillation. This problem is mitigated by the retort method because the starting pore volume is as-received,
meaning that the as-received fluids are still in the rock, and any associated salts are still dissolved in the pore water, so we
don’t have to account for them in the measurement of pore volume. We do not know if the lab that conducted the Dean Stark
experiments did a chloroform-methanol extraction
after the toluene extraction to remove any salts that
could be inhabiting the pores at the time they conduct
their porosimetry measurements. Even if they did not,
this does not explain the fact that they actually
recovered more water than the retort method did.
Additionally, we unfortunately do not have post-Dean
Stark XRD data from the other lab.

In addition, for unconventional reservoirs, the overall

volumes of pore and water are very small, typically
<1-1.5 cc each for commercial-sized samples
(typically <= 50 g). The consequence of this is
apparent in figure 6, which shows the relationship
between the retort-measured clay-bound water and
measured water saturation difference between Dean
Stark and retort. The trend at first seems counter-
intuitive; the less the clay-bound water, the greater the
Figure 6: Relationship between retort-derived clay-bound water and
saturation difference. However, what this also
the difference between Dean Stark and retort water saturations.
suggests is that the lower the amount of extractable
water in the system in the first place, the greater the error that can result due to the precision of the measurement. In other
words, a measurement error of only 0.2 cc (for example) in either pore volume, water volume, or a combination of both will
have a much greater influence on the water saturation than if there were more extractable water. With the uncertainties in salt
precipitation (or potentially other effects) in the post-Dean Stark porosimetry measurements, this could produce large
experimental error. Furthermore, this need not be purely attributed to measurement precision or error, but could be do to
inconsistent water release intrinsic to the rock being tested. As mentioned earlier, retort, at least, extracts what it defines as
“total water” at a consistent point within the water release continuum (against temperature). It is less clear the degree to
which Dean Stark can be equivalently consistent, considering the introduction of wetting solvents and the amount of time it
takes to conduct the experiment at elevated temperature. In addition, the Dean Stark method has to reconcile the water
recovered in the receiver vessel with the mass lost from the sample. Typically such a mismatch is attributed to oil still
dissolved in the toluene, and calculated as oil saturation; however, with the overall small volumes of fluids extracted, small
pore volumes, and small mass losses, the potential for large error is present, as suggested by figure 6.

In a conventional reservoir, with high porosity, and consequently high pore volume, a 0.2 cc (for example) error would likely
barely have an effect. In a 5% porous unconventional shale sample, with a bulk density of 2.5 g/cc and a 50 g sample, the
pore volume would be 1 cc. If the porosity were 25% (not atypical for a conventional reservoir), the pore volume would be 5
cc. Therefore, the 0.2 cc measurement error would be a 20% saturation difference in the unconventional rock, and 4%
SPE 159976 7

saturation difference in the conventional rock. The average Dean Stark sample mass was ~40g, with an average of ~0.5 cc
fluid extracted and ~1.5 cc pore volume, and the retort sample masses were 27 g, with average ~0.15 cc fluid extracted
through the second temperature step and pore volume on average ~0.75 cc.

Validation of retort water volumes

To provide additional reference points for comparing the extracted “total” water (i.e., not including structural water), we
performed two additional sets of experiments: Thermogravimetric Analysis (TGA), and an anhydrous solvent extraction Karl
Fischer titration method. We used the same TGA device as was used in Handwerger, et al., 2011 to recover water from splits
of the same 28 samples used for commercial retort and GRI/Dean Stark analyses.

We also ran splits of the same 28 samples through a Karl Fischer Assay using methanol extraction. This is a completely
different methodology to either Dean Stark or retort, in that it is performed at room temperature using a hygroscopic solvent
and so is an independent check on the results. Briefly, in the Karl Fischer experiments, water was quantitatively extracted
from a comminuted rock sample in a sealed container using a large excess of anhydrous methanol. The water content in the
methanol was determined using the Karl Fischer technique (API Standard 40). All steps in this method are performed in
sealed containers and a glovebox to prevent contamination from atmospheric moisture.

Figure 7 shows a comparison of the water volumes recovered in retort, Dean Stark, TGA and Karl Fischer experiments. The
smallest water volumes shown, labeled “retort T1” represent the amout of free water recovered from the samples at the first
retort temperature (110 ˚C). There is no analogue in either Dean Stark or Karl Fischer experiments, and we did not subdivide
the low-temperature hump of the TGA into separate phases, as our point of comparison to other methods is the cumulative
amount of water in the first hump. However, the collection of water volumes grouped around the “retort T2” data show that
retort, TGA and Karl Fischer all recovered about the same amounts of water at the point where total porosities and
saturations should be reported. The fact that we were able to reproduce the “retort T2” water volumes using the higher-
precision (and slightly different) TGA method, and more importantly the Karl Fischer assay, suggests that this does represent
a consistent point in the water-release continuum and is related to the complete recovery of free and loosely-bound clay
water. The Dean Stark recovered water volumes are, as we already know, significantly higher.

It is worth noting, however, that the water

recovered from the series of anhydrous solvent
extractions coupled with Karl Fischer does show
slightly elevated values relative to TGA and
retort. As was discussed above in the section on
the Dean Stark method, this result again points to
the fact that a wetting solvent (in this case
methanol) can greatly facilitate recovery of water
from the rock. Furthermore, in addition to
recovering the water, the methanol also dissolves
at least some of the salts that are present in this
rather saline rock. That salt maintains an affinity
for the water in the system, and as already
mentioned, the more water one extracts, the
harder it is to mobilize the next slug of water. It
is likely in this case that the residual salts are still
holding on to some small fraction of the in-situ
water during the retort and TGA extractions.

Figure 7: Comparison of water recovery from retort, TGA, Karl Fischer Since the Karl Fischer assay uses methanol, the
assay and Dean Stark experiments on the same 28 samples. Note the salts are effectively removed from the system,
agreement between retort, TGA and Karl Fishcer at the retort T2 level along with the water, in this technique. Even
(total porosity and saturation)and the agreement between retort and TGA considering this artifact, the Karl Fischer water
at the retort T3 (extraction of structural/hydroxyl water). Further note volumes are much closer to the retort T2 water
that the Dean Stark water volumes are between the two.
volumes than they are to the Dean Stark recovered
water volumes, or certainly than the Dean Stark water volumes are to the retort/TGA water volumes.

Lastly, the highest water volumes were, unsurprisingly, recovered at the retort T3 temperature. The TGA experiments show
similar amounts of water at that temperature as well. Neither Karl Fischer nor Dean Stark should be extracting any of this
water, yet the Dean Stark water volumes do lie between the retort T2/TGA T1/Karl Fischer volumes and the high temperature
volumes. This does suggest that somehow the GRI protocol could be “poaching” some of the structural/hydroxyl water. If
8 SPE 159976

this were the case, then it would explain the elevated total water saturations AND elevated total porosities, as this excess
water should contribute to neither. If it were not know that this was happening, and the Dean Stark water volumes were
taken “as is”, then the calculations for total saturation and total porosity would not be representing the true state of the rock.

Comparison to XRD

Figure 8a shows the relationship between retort reported clay-bound water, which includes the sum of both
interlayer/capillary and structural/hydroxyl water, and the bulk sample total clay abundance as measured by XRD for the 28
samples (retort T1 water, considered “free water”, is not included). Figure 8b shows the relationship between actual
recovered water volumes during retort (excluding T1 water) and XRD total clay. Since the retort method uses samples of all
the same mass, there is no need to normalize the water volumes per gram of sample in this case (conversely, the Dean Stark
method samples were all different masses). The strong correlations show that a) retort is an effective means to separate free
from clay-bound fluids, and b) retort clay-bound water measurements are a useful proxy for clay abundance. This does not
seem to be the case with the Dean Stark measurements, as illustrated by figure 9. The much weaker correlation between
recovered Dean Stark water and XRD total clay is partially misleading, however. Since the Dean Stark experiment cannot
separate free from capillary-bound clay water, the water plotted in figure 9 is the sum of both fluids. A better correlation to
XRD total clay might exist if there was an additional correlation between free and capillary-bound water, such that both
would track each other and variation in one, translated to a variation in the other, would further be correlative to the amount
of clay in the sample. But such a correlation does not necessarily exist, so that the weaker correlation between Dean Stark
water and XRD total clay could be partially due to obfuscation caused by an independent free water volume. Indeed, the fact
that the best-fit line to these data has a positive Y-intercept value, and the R2 value does not improve when the regression line
is forced through (0,0) suggests that the Y-intercept value could be the average free water contribution to the total water
recovered in the experiments. It should be reiterated that this is an average value. We are not suggesting here that such plots
could form the basis for determining the free water contribution to recovered Dean Stark water on a sample-by-sample basis.

Figure 8: Relationship between retort recovered clay-bound water and bulk clay abundance from XRD. The difference between
(a) and (b) is that (a) is normalized by the bulk volume of the sample.

Regardless, the volume of water attributed to capillary/interlayer water is a significant portion of the whole, and as a result,
we might expect a better correlation. The fact that is not the case suggests the addition of another non-uniform source of
water, either “poached” from the structural/hydroxyl water (though not a consistent amount) or external contamination, or a
combination of both.

Figure 10 shows the comparison between the excess amount of recovered Dean Stark water (relative to what retort
recovered), per gram of sample, and the total clay abundance in bulk sample, as determined by XRD. The correlation here is
better than that of figure 9. This suggests that the Dean Stark experiment could indeed “poaching” some fraction of the
structural/hydroxyl water in the clays, because the excess amount of water Dean Stark seems to be recovering is correlative to
the clay abundance. If the source of excess water was purely external contamination, there is no reason to believe there
would be such a correlation. There may be some amount of external contamination, or else the correlation might be better,
but that does not seem to be the dominant effect. It could also be due to the fact that each Dean Stark experiment is
performed in a different apparatus, potentially under slightly different conditions, over slightly different amounts of time, and
that could also be affecting the strength of the correlation by liberating non-predictable amounts of structural/hydroxyl water.
The retort experiments, in contrast, were all done in batch – under the same heating and timing conditions, in the same
apparatus, and at the same time.

Gas-filled porosity
SPE 159976 9

What we have shown above is that the excess water recovered by Dean
Stark over retort manifests itself as higer water saturation and higher
porosity. However, the most relevant parameter, especially for
calucalting gas in place, is the gas-filled porosity. The gas-filled
porosity, mathematically, is the product of gas saturation and porosity
(water-filled porosity would be the product of water saturation and
porosity, and oil saturation would be the product of oil saturation and
porosity, such that the sum of these three “partial” porosities would be
equal to the overall porosity). If the porosity is total porosity, then the
saturation must also be total saturation, and if the porosity being used is
effective, then the saturation needs to be effective as well. Regardless,
the gas-filled porosity should be the same, one just needs to be
consistent in the inputs. In the Dean Stark experiment, the gas-filled
porosity is calculated as just illustrated, and the pore volume is
measured after the rock is cleaned of fluids. In retort, the gas-filled
porosity is directly measured, and is in fact the initial pore volume (of Figure 9: Relationship between the amount of water
as-received rock) to which the volumes of extracted fluids are added recovered during Dean Stark and the amount of
(increasing pore volume as fluid is removed), and saturations and clay in bulk sample. Note the poorer correlation
porosity are calculated. However, regardless, if Dean Stark measures relative to the similar figure for retort recovered
excess water saturation and excess porosity as a result, theoretically, the water (Figure 8). This is slightly misleading because
product of the two (actually, the product of porosity and 1-Sw, assuming the Dean Stark method cannot separate free from
bound water, but as a result, the existence of a
no oil saturation, as is the case here) should cancel out and yield the positive Y-intercept (black line) on the best-fit
same gas-filled porosity measured by retort. relationship suggests the average free water content
for the 28 samples.
Figure 11 shows the comparison between the Dean Stark and retort gas-
filled porosities in the 28 companion samples. What is apparent is that
the relationship is quite a bit closer than with water saturation and total
porosity, so in some respect, the above discussions have been academic
because the most relevant parameter is the most similar. Yet, at higher
gas-filled porosity values, the Dean Stark method still produces a
significantly elevated gas-filled porosity, about 50% higher than from the
directly measured retort protocol value. Since it is at the high end of gas-
filled porosity that we have a resource, this is the critical area, and is the
area with the largest discrepancy.

The question then becomes, why does this occur? We suggest that the
difference here is the result of low clay volume, following logic similar
to the explanation of figure 6 above. The region of highest gas-filled
porosity in this reservoir section has the lowest clay content (measured
by XRD). Consequently, the amount of available water is also less,
which amplifies the error in calculated water saturation and porosity.
Figure 10: Relationship between bulk clay
Furthermore, if the excess water is not translated to excess pore volume
abundance and the amount of excess water
recovered by Dean Stark relative to retort. The
directly, as would be the case if the excess water were either external
relationship is better than that in figure 11, but the contamination or from the structural/hydroxyl water in the clays, then the
spread seems to increase at higer clay contents. The imact on porosity and saturation ceases to be 1:1, leading to excess gas-
R2 improves to 0.61 if the obvious outlier is filled porosity as well when you multiply them together (or more
removed. correctly, 1-Sw by porosity).

Correcting for the excess Dean Stark water volumes

Any useful correction to translate Dean Stark measurements to retort-equivalent measurements would require using inputs
only provided by the Dean Stark method. If one had retort measurements on all samples, then obviously no correction would
ever be needed. One could use the relationships shown in figures 4b & d, but those relationships do not provide any insight
into what the source of the differences between the two methods could be. Our goal here is to try to avoid the simple
correlation and get to the roots of the discrepancies, then use some reasonable petrophysical interpretations to provide a more
robust relational method.

If the excess water that Dean Stark recovers relative to retort comes from the clays, then the XRD clay volume would be a
logical source of correction to bring Dean Stark method data into line with retort data. To this end, figure 12 suggests a
10 SPE 159976

correlation between the actual volume of water Dean Stark recovers in excess to retort. This correlation could then be used
on XRD total clay volumes to “predict” the amount of excess water Dean Stark is recovering, assuming it’s all “poached”
from the structural/hydroxyl phase. The correlation is statistically relevant, even if not as strong as that between retort clay-
bound water and XRD total clay, but if there is atmospheric contamination or other experimental artifacts, they would be
difficult to correct for a priori. By predicting the amount of excess water Dean Stark is likely extracting, then one can correct
to the amount of water retort would recover. From there, knowing the starting pore volume from He-porosimetry experiment
done before retort (not to be confused with the pore volume measurement made during the GRI protocol, after Dean Stark
extraction), one can recalculate the porosities and saturations.

Figure 11: Comparison of retort and Dean Stark
method gas-filled porosity. Note that this
relationship is closer to 1:1, and with higher R2
than either total porosity or total water saturation.porosities and saturations from the retort experiment (Handwerger, et al.,
disproportionate v/v relationship. Basically, structural/hydroxyl water does not occupy pore space.
Of course, if one does not actually have pore volume measurements made
prior to Dean Stark (other than through an experimental companion data
set, as shown here to build the correlation), then that would also need to
be corrected. The basis for this correction is shown in figure 12, where
the excess pore volume (Dean Stark vs. companion retort samples) is
plotted against the original reported Dean Stark pore volume. This was
the best relationship we could find to account for the excess pore volume
Dean Stark was measuring. We suggest that if the nature of this excess is
in the fact that structural/hydroxyl water, it should not count as pore
volume in the first place, such that the pore volumes calculated from the
original Dean Stark data are wrong – and the error is a function of the size
of the pore volume. Also note that the slope of the best-fit line suggests
that, unlike for free or capillary-bound water, 1 cc of water recovered as
structural/hydroxyl water is not a 1 cc increase in pore volume. This 1:1
assumption is standard for calculating porosity, and is used for computing
2011), but cannot be applied in this case. Since we are correcting for an
assumed structural/hydroxyl phase of water, we have to account for this

With excess water volumes computed from XRD clay abundance, and retort-equivalent water volumes subsequently
calculated, followed by excess pore volumes computed from the pore
volumes originaly measured using Dean Stark (and retort-equivalent
pore volumes calculated), it is a simple matter to recalculate the total
water saturation and total porosity using the standard equations (see
appendix).

To correct for gas-filled porosity, all that is subsequently required is to

take the corrected total water saturation and multiply it by the corrected
total gas saturation (1-Sw, assuming no oil).

Cautionary note

The equations shown here are for one particular thermogenically mature
gas shale in the US. Consequently, they likely only apply to this one
particular example. No two shales are equivalent. It doesn’t matter
whether two shales are both “siliceous mudstones”, or both “argillaceous
mudstones”, there will always be compositional and/or textural
differences (e.g. Sondergeld, et al., 2010b; Gathogo, 2011) that will Figure 12: Relationship between excess pore
affect the continuum of water release. Despite this, as long as the shales volume from post-Dean Stark porosimetry
are not overly smectitic, retort captures a very consistent water release measurement and calculated pore volume from
spectrum. It is not clear that Dean Stark does the same. As a result, the pre-retort porosimetry measurement and sum of
corrections applied here should not be taken in any way as globally evolved water at retort T2. They should be
relevant. What we hope we have illustrated is a workflow to determine equivalent, but are not. The offset seems to be a
corrections relevant for different shales that consists of gathering a set of loose function of the Dean Stark measured pore
correlative GRI, retort and XRD data to determine similar relationships volume. This allows for a correction based solely
on the Dean Stark data (once the relationship is
elsewhere. The example here shows relationships based on samples from known).
multiple cores combined into a single data set, suggesting the
applicability of these corrections to a large area in this field.
SPE 159976 11

Additionally, the example shown here is for a two-fluid rock: gas and water. In liquid hydrocarbon rich shales, the presence
of the oil will provide additional complication, least of all because oil saturation is inferred in Dean Stark, while it can be
directly observed in retort (Handwerger, et al., 2011), though under as-received conditions. As a result, phase change in the
oil during recovery from the subsurface also has to be considered. This would suggst a need to gather PVT data as well,
though if the PVT effects are consistent (e.g. the oil chemistry is not highly variable), then corrections would be to surface
conditions. Otherwise, a decision would need to be made as to whether to simply correct for a total hydrocarbon saturation,
but that is complicated by the measured oil saturation, as its volume contribution needs to be accounted for separately from
water due to the density difference.

Conclusions

There has been much discussion about differences between the two main analytical methods used to measure saturations and
porosities in tight shale gas reservoir rocks, without much attempt to understand the nature of these descrepancies. We have
assembled a data set in one particular thermogenic shale gas play, based on samples from multiple cores across the basin, to
try and find a means to correlate between data collected using these two techniques – retort and Dean Stark.

The data set we assembled confirms the general industry-wide observation that data from the Dean Stark method show higher
water saturation and porosity than data generated via retort analysis. While the data are generally qualitatively correlative
(figure 4), they disagree quantitatively, often significantly, and this could bias the calculation of reserves to higher estimates
if the effects do not cancel each other out; hydrocarbon filled porosity being the product of total porosity (too high) and
hydrocarbon saturation (too low, as it is 1- Sw). By reverting to basic petrophysical parameters – the data actually collected
(water and pore volume, and rock bulk volume) – rather than the resultant values of porosity and saturation, we have
observed that the GRI/Dean Stark method physically extracts more water from the sample than retort does at the point of
hypothetical agreement; the total porosity and total water saturation. Furthermore, the retort method measures gas-filled
porosity directly, on as-received sample, and is likely more accurate than the Dean Stark method, which measures a pore
volume after solvent extraction, which could be adversely impacted by the experiment itself.

The amount of excess water recovered via Dean Stark correlates with the amount of clay in bulk sample measured by XRD,
albeit with significant scatter, suggesting the clay as a possible source of this excess, and the possible source of a correction.
Additionally, the amount of excess water is not as high as to be above the total amount of water that could be contributed by
the clays; that is, the sum of both capillary/interlayer water and structural/hydroxyl water, further suggesting a possible clay
source for the excess. While, theoretically, the only water that should be coming from clays in Dean Stark is the loosely-
bound capillary/interlayer clay water, the large amount of time the sample spends bathing in a toluene vapor (potentially
several weeks) and then oven dried, could be affecting the way water is released by the clays through the effects of the
solvent. The Dean Stark method as employed in the GRI protocol could as a result be “poaching” a fraction of the the very
tightly bound structural/hydroxyl clay water.

In contrast, the retort method shows a large reduction in the rate of water release between free+capillary/interlayer water and
structural/hydroxyl water (figures 1 & 2) as a function of temperature, in an essentially non-wetting nitrogen atmosphere
(either air or pure nitrogen). As a result, the water saturations and porosity measured should be consistent from sample to
sample, as well as shale to shale (assuming limited amounts of smectite, gypsum, or other unaccounted for hydrous minerals).
Furthermore, independent measurements of (“total”) water volume made with thermogravimetric analysis or Karl Fischer
assay validate the amount of “total” water recoverted by the retort method, and therefore also show lower recovered water
volumes than Dean Stark. However, it should be pointed out that if the rock is natively highly saline, the retort method may
leave behind some small amount of water due to the affinity of the water to the salts. This would also be the case in Dean
Stark, unless it was followed up by a chloroform-methanol extraction to remove the salts prior to a porosimetry measurement.

Failure to perform a chloroform-methanol extraction prior to a porosimetry experiment post-Dean Stark can lead to incorrect
pore and grain volume measurements because of the impact of the residual salts. This issue is mitigated in the retort method
because the porosimetry experiment is run on as-received sample, prior to any fluid extraction. Increases in pore volume due
to fluids, in the retort protocol, are accounted for by the ability to directly observe and quantify the amount of water (and oil)
extracted from the sample at each step, and then mathematically add the volume to the initial measurement of as-received
pore or grain volume, which also conveniently happens to be a direct measure of gas-filled porosity. In addition, in samples
with low overall recoverable water (i.e. low clay content), lack of experimental precision in either the ability to precisely
measure the recovered fluid volume or the ability to measure a representative pore volume (complicated in the GRI protocol
by doing this after cleaning the sample, when residual salts or mineral alteration are more likely) could propagate as errors in
water saturation and porosity. This can then extend into the calculation of gas-filled porosity.

The route to a correction, therefore, lies in collecting a comparable set of retort and Dean Stark data within a particular shale.
The data needed from each sample are the amount of water recovered from each method, the sample masses, pore (or grain)
12 SPE 159976

volumes, the bulk density, and the clay abundance. From there, a relationship betwteen the water volume difference and total
clay from XRD can be determined and used to correct the Dean Stark water volume to a retort equivalent “total” water
volume. For pore volume, the relationship is between the excess GRI-protocol pore volume vs retort and the actual measured
GRI pore volume. This is because 1 cc of excess extracted water does not translate into 1 cc of excess pore volume. The
source of the excess water is likely the structural/hydroxyl water in the clays, and this does not correlate to a 1:1 pore volume
excess. With a corrected water volume based on the clay abundance, and a corrected pore volume based on the pore volume
measured using the GRI protocol, the basic petrophysical math used in the retort method can be applied to bring the two data
sets in line.

However, we strongly caution against using any such derived correlations/corrections globally. Each shale, despite potential
mineralogic similarities, is different enough in its clay abundance, clay mineralogy and textural aspecs that no one
relationship or set of relationships will likely be valid in other shales. Also, the addition of liquid hydrocarbons will
introduce its own set of complications, but that is a topic for another paper. Either way, a liquids-rich shale methods-
correlation workflow should follow similar bounds, with the additional need to collect PVT data, or live with the
consequences of phase change as the core is brought to the surface.
SPE 159976 13

References:

American Petroleum Institute (API). 1998. Recommended Practices for Core Analysis, Recommended Practice 40, Second Edition. API,
Dallas, TX.

Coussy, O., 2010, Mechanics and Physics of Porous Solids, John Wiley and Sons Inc. pp 132-135.

Gathogo, P.N., Diagenetic Transformations of Tight Shales. 2011. Monograph of the First Shale Science Conference “Evolution of the
Mental Picture of Tight Shales, 28-29 March, Warsaw, Poland.

Handwerger, D.A., Suarez-Rivera, R., Vaughn, K.I., and Keller, J.F., 2011. Improved Petrophysical Core Measurements on Tight Shale
Reservoirs Using Retort and Crushed Samples, SPE Paper 147456 presented at the SPE Annual Technical Conference and Exhibition,
30 October – 2 November, Denver, CO, USA.

Jury, W.A., Gardner, W.R., Gardner, W.H., 1991. Soil Physics, 5 th Ed. John Wiley and Sons Inc. pp 61-64.

Luffel, D.L., and Guidry, F.K., 1989. Reservoir Rock Properties of Devonian Shale from Core and Log Analysis. Paper 8910 presented at
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Petroleum Tech. pp. 1184-90.

Nguyen-Huynh, D., Hemptinne, J.C., Lugo, R., Passarello, J.P., Tobaly, P., Modeling Liquid-Liquid and Liquid-Vapor Equilibria of
Binary Systems Containing Water with an Alkane, an Aromatic Hydrocarbon, an Alcohol or a Gas (Methane, Ethane, CO 2 or H2S),
Using Group Contribution Polar Perturbed-Chain Statistical Associating Fluid Theory, Ind. Eng. Chem. Res. 2011, 50, 7467–7483

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Sondergeld C.H., Newsham, K.E., Comisky, J.T., Rice, M.C., and Rai, C.S. 2010a. Petrophysical Considerations in Evaluating and
Producing Shale Gas Resources, SPE Paper 131768 presented at the SPE Unconventional Gas Conference, 23-25 February,
Pittsburgh, PA, USA.

Sondergeld, C.G., Ambrose, R.J., Rai, C.S., and Moncrieff, J. 2010b. Micro-Structural Studies of Gas Shales, SPE Paper 131771 presented
at the SPE Unconventional Gas Conference, 23-25 February, Pittsuburgh, PA, USA.

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14 SPE 159976

Appendix: Mathematical calculations.

Initial measurement is b in order to determine bulk volume (Vb ): (Vb = m/b)

Both methods measure volumes of fluids Vp = (Vf), where Vp is pore volume and Vf is fluid volume (both oil and water)
 is Vp/Vb
Sw is Vw/Vp (Vw is water volume)

In the case of Dean Stark:

 = Vp/Vb (pore volume is measured after extraction)
Sw = Vw/Vp

In the case of retort, more fluid phases are discriminated:

 g is Vg/Vb (from He-porosimetry) (Vg is volume of gas)
 e is (Vg+Vw,T1)/Vb = Vp(e)/Vb (Vw,T1 is water volume at the first retort temperature, T2 at the second, and so on)
 t is (Vg+Vw,T1+Vw,T2)/Vb = Vp(t)/Vb (Vp(e) & Vp(t) are pore volumes for effective porosity or total porosity calculation)
CBW is (Vw,T2+Vw,T3)/Vb (CBW is clay-bound water)
Sw(e) is Vw,T1/(Vg+Vw,T1) = Vw(e)/Vp(e) (Vw(e) and Vw(t) are water volumes for effective and total saturations
Sw(t) is (Vw,T1+Vw,T2)/(Vg+Vw,T1+Vw,T2) = Vw(t)/Vp(t)