SPE-175954-MS

Impact of Solvent-Extraction on Fluid Storage and Transport Properties of

Montney Formation
A. Ghanizadeh, C.R. Clarkson, S. Aquino, A. Vahedian, University of Calgary; O.H. Ardakani, H. Sanei,
Geological Survey of Canada; J.M. Wood, Encana Corporation

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE/CSUR Unconventional Resources Conference—Canada held in Calgary, Alberta, Canada, 20–22 October 2015.

This paper was selected for presentation by an SPE program committee following review of i nformation contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract
Pore and pore-throat blocking materials may have a negative effect on reservoir quality, as has been recently determined for
the low-permeability, hydrocarbon bearing portions of the Montney Formation. Some of these materials, such as salt and
bitumen, may be extractable using different solvents combined with the Dean-Stark extraction process. The primary objective
of the current study is therefore to investigate the impact of solvent-extraction on various geochemical and petrophysical
characteristics of low-permeability intervals. To accomplish this goal, a comprehensive dataset was collected for two sample
suites from the Montney Formation (western Alberta, northeastern British Columbia; Canada), before and after sequential
solvent-extractions with organic solvents.
The samples are analyzed after three different treatments: 1) “as-received”, 2) toluene-extracted and dried, and, 3)
toluene/methanol-extracted and dried. The methods used for characterization of the samples after each treatment are Rock-
Eval pyrolysis (TOC content, S1, S2); helium pycnometry (grain density, porosity); low-pressure gas (N2, CO2) adsorption
(surface area, pore volume, pore size distribution); and crushed-rock gas (He) permeability. Importantly, to ensure a proper
comparison of the different sample treatments, the solvent-extraction and subsequent geochemical and petrophysical analyses
are performed on identical samples; therefore, the effect of sample heterogeneity is mitigated.
The impact of solvent-extraction on grain density, pore network attributes (surface area, pore volume, pore size
distribution) and permeability of the Montney samples depends on the organic matter content, solvent type and other sample-
to-sample variations. For one dataset (batch A), the change in petrophysical properties is variable and not predictable, while
for the other (batch B), grain density, pore network attributes (surface area, pore volume, modal pore size distribution) and
permeability exhibit an increase after sequential solvent-extraction with toluene and methanol. The variability observed for
batch A is possibly attributed to (1) different degrees of salt precipitation, depending on the “in-situ” water/brine content and
the salinity of the “in-situ” (formation) water and/or (2) experimental uncertainties/errors. A detailed discussion of the
experimental uncertainties/errors is provided to elucidate the impact of these factors on the experimental outcomes.
In the current study, it is demonstrated that by applying multiple analysis techniques on two diverse sample suites
subject to three different treatments, the variation in pore structure and fluid flow characteristics of fine-grained tight oil/gas
reservoirs before and after solvent-extraction can be quantified. The quantification of these effects may have important
implications for both shale matrix transport characterization, which usually involves some form of extraction prior to
petrophysical evaluation, and stimulation treatments for improving hydrocarbon recovery by removal of pore-blocking
materials.

Introduction
The Triassic Montney Formation in the Western Canadian Sedimentary basin hosts large resources of tight oil, gas and
liquid-rich gas. Tight siltstone (“unconventional”) reservoirs within the Montney are currently a primary target for many
oil/gas companies in western Canada (Rivard et al. 2014). The Montney Formation is an aerially vast hydrocarbon play
(approximately 130,000 km2) with a thickness commonly ranging between 100 m and 300 m, thickening from less than 1 m
in the east to over 350 m in the west (Rivard et al. 2014; Chalmers and Bustin 2012; Kuppe et al. 2012). The depth of the
Montney Formation increases from approximately 500 m in the east to over 4,000 m in the west (Rivard et al. 2014). This
variation in burial depth has led to the generation of various phases of hydrocarbon from east to west including oil,
condensate and dry gas (Rivard et al. 2014; Chalmers and Bustin 2012; Kuppe et al. 2012). Similar to many other
SPE-175954-MS 2

unconventional plays, production forecasts for the Montney Formation remain a challenge due in part to its subsurface
heterogeneity and complexity. Economic hydrocarbon flow rates in the Montney Formation, with nano- and micro-Darcy
unstimulated (matrix) permeabilities (Ghanizadeh et al., 2015), can only be achieved using drilling/completion technologies
such as multi-fractured horizontal wells (MFHW). Though short-term production is primarily controlled by hydraulic
fractures and the performance of MFHWs, long-term production is controlled by matrix permeability. The ability of industry
to optimize recovery in the Montney is still limited by insufficient understanding of the effect of different controlling factors
including “in-situ” fluid properties and degraded solid bitumen on porosity and permeability.
The impact of thermally degraded solid bitumen on reservoir quality of unconventional tight oil and liquid-rich gas
reservoirs has become increasingly recognized in recent years (Wood et al., 2015; Haeri-Ardakani et al., 2015; Mastalerz et
al., 2013; Bernard et al., 2012a, 2012b). Through the use of organic petrography and Rock-Eval pyrolysis (Sanei et al., 2015;
Wood et al., 2015), it is been determined that the organic matter in the Montney Formation initially migrated as a liquid oil
phase into the larger paleo-intergranular pore network during hydrocarbon charging. This liquid oil phase degraded later
diagenetically and thermally with increasing burial depth and cracked, in-situ, to light hydrocarbon fluids and solid bitumen.
Present-day total organic carbon (TOC) content in the Montney is believed to be almost all in the form of thermally degraded
solid bitumen (Sanei et al., 2015; Wood et al., 2015). Wood et al. (2015) indicated that the reservoir quality of the Montney
Formation is strongly affected by the presence of pore-blocking solid bitumen. Those authors showed that, while there is no
statistically significant correlation between TOC content (bitumen saturation) and porosity in the Montney Formation, the
samples with smaller TOC contents (<1 wt. %) have consistently higher porosity values (˃7.5%). The previous experimental
studies highlight that hydrocarbon generation, cracking, and the formation of solid bitumen can significantly affect the
porosity and permeability of fine-grained sedimentary rocks (Wood et al., 2015; Wood, 2015; Wei et al., 2014; Mastalerz et
al., 2013; Ghanizadeh et al., 2014; Loucks et al., 2012). Nevertheless, very few published experimental data (Kuila et al.,
2014a,b; Wei et al., 2014) are available in literature that compare petrophysical characteristics of the tight oil/gas formations
before and after removal of solid bitumen from the pore network of the rock matrix. This is of particular importance/interest
for a tight formation such as Montney with solid migrabitumen as a pervasive intergranular phase within its pore network
(Sanei et al., 2015; Wood et al., 2015).
Sequential solvent-extraction with toluene and methanol (Dean-Stark method) is a common practice for removal of
“in-situ” fluid from the pore network of conventional reservoirs. Solvent-extraction with toluene is performed to remove “in-
situ” water and residual light hydrocarbons from the rock matrix. Solvent-extraction with methanol (or chloroform-methanol)
is routinely performed to remove salt compounds precipitated after the Dean-Stark distillation process with toluene (API,
1998). Though Dean-Stark extraction is routinely used for conventional reservoirs, the application of this technique for shale
oil/gas and tight oil reservoirs may result in unwanted effects such as dissolution of organic matter (solid bitumen). It has
been reported recently that the application of this technique in unconventional reservoirs, in addition to the removal of “in-
situ” fluids, might also result in the removal of organic matter (bitumen) from the rock matrix (Burger et al., 2014; Wei et al.,
2014). Burger et al. (2014) indicated that the Dean-Stark extraction with toluene is prone to dissolution of a portion of
organic matter that is immobile. This immobile portion of the organic matter is not thermally-extractable below 200 °C, but is
soluble in organic solvents during Dean-Stark extraction. Wei et al. (2014) also used Soxhlet-extraction in refluxing
dichloromethane (DCM) and toluene to remove soluble oil and bitumen from the matrix system of the Devonian-
Mississippian New Albany Shale samples (USA). Application of the Dean-Stark method might also result in the removal of
the structural water from clay minerals (dihydroxylation), according to some experimental studies (Handwerger et al., 2012).
However, other experimental studies (e.g. Burger et al., 2014) have shown that solvent-extraction of rocks with toluene and
methanol at temperatures lower than 200 °C is not affected by the dihydroxylation of clay minerals. Because the presence of
solid bitumen in the pore network of the Montney Formation has been confirmed (Sanei et al., 2015; Wood et al., 2015), it is
expected that the sequential solvent-extraction of the Montney samples with organic solvent (toluene/methanol) results in the
(partial) removal of solid bitumen from the rock matrix.
It has been frequently reported by the industry that the salinity of the produced water from the Montney Formation is
higher than expected (unpublished data). Water-based hydraulic fracturing fluids generally have lower salinity than formation
water, and therefore, the salinity of the produced water typically increases with time. This is particularly the case for the
Montney due to the presence of hypersaline formation water which occurs as free or clay-bound water (Wood, 2013, 2015).
Due to the presence of hypersaline formation water, significant salt precipitation may occur after core retrieval from
subsurface, affecting porosity and permeability. One of the objectives of this study is to compare pore network attributes and
permeability of Montney samples before and after salt removal (methanol-extraction) in order to investigate the possible
impact of salt precipitation on the core analysis results.
This study presents results from an ongoing laboratory study investigating the impact of “in-situ” fluids, degraded
solid bitumen and salt on porosity and permeability of the Montney Formation. The specific objectives of this study are to 1)
quantify the impact of solvent-extractable bitumen on permeability and 2) evaluate the possible impact of salt precipitation
during core retrieval on core analysis results. To accomplish these goals, a comprehensive dataset was collected for two
diverse sample suites from the Montney Formation (western Alberta, northeastern British Columbia; Canada), before and
after sequential solvent-extractions with organic solvents. The samples are analyzed under three different sample treatment
conditions: 1) “as-received”, 2) toluene-extracted and dried, and, 3) toluene/methanol-extracted and dried. The characterizing
techniques used for each sample include Rock-Eval pyrolysis (TOC content, S1, S2); helium pycnometry (grain density,
SPE-175954-MS 3

porosity); low-pressure gas (N2, CO2) adsorption (surface area, pore volume, pore size distribution); and crushed-rock gas
(He) permeability. One of the unique aspects of this study is that solvent-extraction and the subsequent geochemical and
petrophysical analyses are performed on identical samples; therefore, the effect of sample heterogeneity on the outcomes of
the comparisons is mitigated. Through the application of multiple analysis techniques for two diverse sample suites subject to
three different treatment states, the variation in pore structure and fluid flow characteristics of the Montney samples before
and after the removal of pore-blocking organic matter and salt from the rock matrix is quantified.

Samples Used in the Study

A total of 20 crushed-rock samples were analyzed in this study (Table 1). These samples were obtained from two vertical
wells drilled in western Alberta (batch A; 10 samples) and northeastern British Columbia (batch B; 10 samples), penetrating
the Montney Formation. The samples from batch A were obtained by crushing/sieving (20/35 US mesh size, 0.50-0.84 mm)
core plugs with a diameter of 3.8 cm (1.5 inch). Detailed geochemical, petrographic and petrophysical characteristics of these
samples in the “as received” state were previously documented/reported (Ghanizadeh et al., 2015). These samples are
analyzed only in toluene-extracted and methanol-extracted states in this study. The samples from batch B were selected from
a 2/3 slabbed core (sample “chunks”). These sample “chunks” were then crushed/sieved (20/35 US mesh size) to obtain the
crushed-rock material portions and analyzed in “as-received”, toluene-extracted and methanol-extracted states in this study.
“As-received” in the context of this work means that the samples were tested without any further treatment in the laboratory
after drilling/crushing.

TABLE 1 – ORIGIN, NUMBER, DEPTH AND MOISTURE CONDITION OF THE ANALYZED SAMPLES

Batch ID Origin/Locality Number of samples Depth interval (m) Analyzed condition

batch A western Alberta 10 3,042.54 – 3,145.68 solvent-extracted

batch B northeastern British Columbia 10 1,972.27 – 2,000.25 as-received & solvent-extracted

Experimental Workflow and Techniques

Laboratory protocols, including the list of experimental techniques and sequence of measurements is shown in Fig. 1. The
samples are analyzed in three states: 1) “as-received”, 2) toluene-extracted and dried, and, 3) toluene/methanol-extracted and
dried.

Fig. 1 — Laboratory protocols including the list of experimental techniques and sequence of measurements. For each test, the
number of samples analyzed from each batch is indicated. Rock-Eval pyrolysis was performed at Geological Survey of Canada,
Calgary.

After measuring geochemical/petrophysical properties in the “as-received” state, the samples were cleaned in
refluxing toluene (boiling temperature 111 °C) using the Dean-Stark method (10 days) to remove solvent-extractable oil,
soluble bitumen, and dried (110 °C; 10 days). After measuring geochemical/petrophysical properties in the toluene-extracted
SPE-175954-MS 4

state, the samples were cleaned in refluxing methanol (boiling temperature 64.7 °C) to remove salt compounds and dried (110
°C; 10 days). The common “best practise” for solvent-extraction duration is approximately 7 days of extraction followed by 7
days of drying (110 °C) - in this study we performed the solvent-extraction for 10 days followed by 10 days of drying (110
°C).
Rock-Eval pyrolysis and low-pressure gas (CO2, N2) adsorption tests were performed only on batch A. Rock-Eval
pyrolysis was performed using a Rock-Eval 6 (Vinci Technologies, France) on all samples in the “as-received” state and five
selected samples after sequential solvent-extraction. The theory and detailed description of the pyrolysis using the Rock-Eval
6 is given in Behar et al. (2001). Low-pressure gas (CO2, N2) adsorption analyses were performed using a 3Flex Surface
Characterization Analyzer (Micromeritics®) for the purpose of estimating surface area, pore volume and pore size
distributions (PSDs) in the micropore (pore size < 2 nm), mesopore (2nm < pore size < 50 nm) and smaller macropore (50
nm < pore size < 200 nm) range. The low-pressure CO2 and N2 adsorption analyses were conducted at 0 °C (273.15 K) and -
196 °C (77.15 K), respectively. Prior to the analyses, the crushed-rock samples (2 g) were degassed overnight in a
temperature-controlled vacuum set-up at 60 °C. The CO2 adsorption data were interpreted using the Brunauer–Emmett–
Teller (BET; Brunauer et al., 1938) and Langmuir models for surface area, the Dubinin–Astakhov (D–A; Dubinin and
Astakhov, 1971) and Dubinin–Radushkevich (D–R) models for micropore volume and Density Functional Theory (DFT)
equation analysis for pore size distributions. The N2 adsorption data were interpreted using multi-point BET and Langmuir
analysis for surface area and Barrett–Joyner–Halenda (BJH; Barret et al., 1951) analysis for pore size distributions. Under
unconfined conditions, porosity values were determined from the skeletal volumes/densities measured by helium pycnometry
using an AccuPyc II 1340 (Micromeritics®), and bulk volumes/densities from either calipered dimensions of cylindrical plugs
before crushing (batch A) or by the Archimedes technique (batch B) in the “as-received” state. Crushed-rock gas (He)
permeability measurements were performed with a SMP-200TM (CoreLab) matrix permeameter using a mean gas (He)
pressure of 1,480.3 kPa (214.7 psia). The crushed-rock gas (He) permeability values were not corrected for the slip-flow
effect. Gas pressures in SMP-200 TM permeameters were recorded using analogue pressure gauges (Setra Systems Inc., USA)
with an accuracy of ±0.11% of the full-scale value of 1.72 MPa (250 psig).

Results
The results of Rock-Eval pyrolysis performed on samples from batch A for the three different sample treatments are listed in
Table 2 (“as-received”; 10 samples) and Table 3 (toluene-extracted and methanol-extracted; 5 samples). The studied samples
are organic-lean (< 0.7 wt. % TOC content) with Tmax values ranging between 376 and 449 °C. A mean equivalent vitrinite
reflectance of about 1.2% was estimated for these samples in the “as-received” state previously (Ghanizadeh et al., 2015).
Petrographic observations performed on the “as-received” samples also indicate that most samples contain very small
amounts of bitumen as the only maceral. Intergranular porosity is commonly filled with degraded oil/bitumen. The results of
Rock-Eval pyrolysis performed on toluene-extracted and methanol-extracted samples confirm that TOC content, and S1 and
S2 peaks (Fig. 2) on the pyrograms progressively decrease with sequential solvent-extraction using toluene and methanol.

TABLE 2 – THE RESULTS OF ROCK-EVAL PYROLYSIS ON AS-RECEIVED SAMPLES

TOC (wt. % S1 S2
Sample No Depth (m) Tmax (°C) HI
HC) (mg HC/g dry rock) (mg HC/g dry rock)
#2A 3,043.05 0.19 436 0.37 0.07 37.00
#3A 3,043.64 0.17 417 0.15 0.02 12.00
#4A 3,044.18 0.32 440 0.65 0.32 100.00
#6A 3,083.61 0.24 451 0.32 0.12 50.00
#7A 3,084.10 0.67 438 1.31 0.76 113.00
#8A 3,084.95 0.37 415 0.97 0.56 151.35
#9A 3,137.23 0.18 376 0.45 0.14 77.78
#10A 3,138.28 0.66 448 0.79 0.61 92.00
#12A 3,139.90 0.14 436 0.22 0.07 50.00
#14A ,
3,145.02 0.84 458 1.73 0.84 100.00

TABLE 3 – THE RESULTS OF ROCK-EVAL PYROLYSIS ON SOLVENT-EXTRACTED SAMPLES

Toluene-extracted Methanol-extracted
Sample No Depth (m) S1 S2 S1 S2
TOC (wt. Tmax TOC (wt. Tmax
(mg HC/g (mg HC/g HI (mg HC/g (mg HC/g HI
% HC) (°C) % HC) (°C)
dry rock) dry rock) dry rock) dry rock)
#2A 3,043.05 0.16 411 0.03 0.05 31 0.12 419 0.01 0.00 0
#3A 3,043.64 0.09 441 0.02 0.04 44 0.07 436 0.00 0.00 0
#7A 3,084.10 0.45 436 0.03 0.18 40 0.45 434 0.01 0.07 16
#10A 3,138.28 0.53 430 0.10 0.20 38 0.53 436 0.00 0.08 15
#14A 3,145.02 0.55 430 0.07 0.20 36 0.52 437 0.00 0.09 17
SPE-175954-MS 5

Fig. 2 — Progressive decrease of S1 and S2 peaks with sequential solvent-extraction.

Low-pressure gas (CO2, N2) adsorption analyses were performed for all samples from batch A, however only the
results for two selected samples (#3A, #14A) are shown in Figs. 3-4. These two samples represent a range in TOC content,
with sample #3A having a low TOC content (0.17 wt. %; Table 2) and sample #14A having a high TOC content (0.84 wt. %;
Table 2). The low-pressure gas adsorption (LPA) data obtained for these two samples are representative of the LPA data
collected for other samples with low and high TOC contents.

Fig. 3 — (a) CO2 adsorption isotherms; (b) CO2 cumulative pore volumes; (c) CO2 dV/d(W) plots; (d) and CO2 dV/dlog(W) plots for
selected Montney samples subjected to three different sample treatments. Plots (b), (c), and (d) were generated using the DFT
method applied to the adsorption branch of the isotherms. Other models such as NLDFT and Horvath-Kawazoe provided similar
results to DFT.
SPE-175954-MS 6

Langmuir adsorption isotherm behaviour is not observed in all cases (Fig. 3a). This observation is likely due to the very low
volume of micropores (< 2 nm) in these samples. Figs. 3b-d illustrate the pore size distributions obtained using the DFT
method for slit-shaped pores. The micropore volume increases with sequential solvent-extraction for all samples. The
increase in micropore volume is more significant for the sample with higher TOC content (Figs. 3b-d). Similar observations
were obtained for other samples. It should be noted that the LPA instrument is capable of detecting low CO 2 adsorption
capacities down to 0.001 cm3/g. This is particularly important for samples analyzed in this study with comparatively low CO2
adsorption capacity (#3A). The repeated LPA analysis for sample #3A showed similar CO2 adsorption capacities.
N2 isotherms (Fig. 4a) show hysteresis between the adsorption and desorption branches, indicating the presence of
meso-porosity (2 nm < pore sizes < 50 nm). PSDs calculated using the N2 adsorption branch and the BJH method (Figs 3b-
3d) are dominantly unimodal. The dV/dlog(W) plots (Figs. 4c-d) suggest uniform PSDs within the mesopore range. BET
specific surface areas measured using the three sample treatments range between 0.3 and 6.5 m2/g. Similar to CO2 adsorption
data, the mesopore and macropore volumes increase progressively with sequential solvent-extraction for all samples (Fig.
4b). The increase in mesopore and macropore volumes is more significant for the samples with higher TOC contents.

Fig. 4 — (a) N2 adsorption isotherms; (b) N2 cumulative pore volumes; (c) N2 dV/d(W) plots; (d) and N2 dV/dlog(W) plots for selected
Montney samples subjected to three different sample treatments. Plots (b), (c), and (d) were generated using the BJH method
applied to the adsorption branch of the isotherms.

Grain density values measured under unconfined conditions for the three sample treatments are shown in Fig. 5. For
batch A, the measured grain density values in “as-received”, toluene-extracted and methanol-extracted states range between
2.71 and 2.78 g/cm3. For batch B, the measured grain density values in “as-received”, toluene-extracted and methanol-
extracted states range between 2.66 and 2.80 g/cm3. While there is no particular relationship between grain density values
measured for batch A in the different states, the grain density values measured for batch B progressively increase with
sequential solvent-extraction.
The crushed-rock permeability values measured with helium for the three different sample treatments stages for
batches A and B are shown in Fig. 6. For batch A, the crushed-rock permeability values measured with helium under “as-
received”, toluene-extracted and methanol-extracted conditions range between 0.7 and 43 nD (7·10-7 - 4.3·10-5 mD). For
SPE-175954-MS 7

batch B, the crushed-rock permeability values measured with helium under “as-received”, toluene-extracted and methanol-
extracted states conditions range between 0.29 and 210 nD (2.9·10-7 - 2.1·10-4 mD). While there is no particular relationship
between permeability values measured for batch A in the different states, the permeability values measured for batch B
progressively increase with sequential solvent-extraction.

Fig. 5 — Grain density values measured for batches A and B after three different sample treatments.

Fig. 6 — Crushed-rock permeability values measured for batches A and B after three different sample treatments.

Discussion
Impact of solvent-extraction on geochemical parameters (TOC, S1, S2). Total organic carbon is composed of a mixture of
different organic compounds. Based on the solubility in organic solvents, organic compounds are subdivided into bitumen
(soluble) and kerogen (insoluble). Hydrocarbon generation from organic compounds in source rocks occurs in three main stages
(Jarvie et al., 2007): (1) the conversion of kerogen to bitumen and gas; (2) the conversion of bitumen to oil; and (3) the
conversion of oil and bitumen to pyrobitumen and gas. Depending on the nature/composition of solvent and organic matter,
solvent-extraction generally results in the removal of the volatile and non-volatile hydrocarbons including the components
within the range of C10 – C40+, asphaltenes and polar nitrogen, sulfur, and oxygen (NSO) compounds with high molecular
weights (Kuila et al., 2014b; Larter, 1988). Solid bitumen is generally expected to be soluble in organic solvents. Only a minor
amount of solvent-extractable organic matter is present in pyrobitumen (Wei et al., 2014; Jacob, 1989), which is generated at
higher thermal maturities.
For batch A, the Rock-Eval data indicate that there is a significant loss of the TOC and S2 components after solvent-
extraction with toluene and methanol. Because the majority of TOC in the Montney Formation is composed of solid bitumen
(Sanei et al., 2015; Wood et al., 2015), it is therefore reasonable to consider that the removal of S2 component after solvent-
extraction is an indication that solid bitumen has been effectively dissolved during toluene/methanol extraction processes.
Table 4 lists the weight percentage estimations of dissolvable organic matter (convertible carbon) that is present in the matrix
of the samples at each state. To estimate the weight percentages of dissolvable organic matter (convertible carbon) at each
SPE-175954-MS 8

state (wt. %), the S2 values at each state were normalized by multiplying by 0.083, which is derived from the average weight
percent of carbon in hydrocarbons by conversion from milligrams of hydrocarbon per gram of rock (Jarvie, 1991). Compared
to the “as-received” state, the toluene-extraction process results in organic matter extractions ranging between 29 and 76%
(Table 4). The methanol-extraction almost completes the dissolution of organic matter with extractions, ranging between 87
and 100% (Table 4). For three samples (#7A, #10A, #14A) more than 65% of dissolvable organic matter (convertible
carbon) extractions occur after toluene-extraction. For one sample (#2A), however, the major dissolution of organic matter
(convertible carbon) occurs after methanol-extraction.

TABLE 4 – THE REMOVAL OF DISOOLVABLE ORGANIC MATTER FROM SAMPLES AFTER SOLVENT-EXTRACTION
Dissolution of organic matter after solvent
Sample Depth Bulk density Dissolvable organic matter (wt. %)
3 extraction (%); compared to as-received state
No. (m) (g/cm ) Toluene-extracted Methanol-extracted
As-received Toluene-extracted Methanol-extracted
#2A 3043.05 2.665 0.006 0.004 0 29% 100%
#3A 3043.64 2.710 0.002 0.003* 0 - 100%
#7A 3084.10 2.618 0.063 0.015 0.006 76% 91%
#10A 3138.28 2.564 0.051 0.017 0.007 67% 87%
#14A 3145.02 2.652 0.070 0.017 0.007 76% 89%
* The observed increase in the amount of dissolvable organic matter (convertible carbon) after toluene-extraction is likely due to the interference of S1 and
S2 peaks measured for this sample (#3A).
The S1 peak from Rock-Eval analysis supposedly represents the residual light hydrocarbon and condensate trapped
within the pore spaces of the rock. For batch A, the S1 values in the “as-received” state are generally low (except for #14A;
Table 2), possibly indicating the minor presence of residual light hydrocarbons in the samples. However, it should be noted
that the S1 peak obtained from the Rock-Eval pyrolysis for unconventional reservoirs can be affected by several factors such
as sample contamination by drilling mud, and other impacts induced by sample storage and preparation (Haeri-Ardakani et
al., 2015; Jiang et al., 2015). Using a compositional thermal analytical technique (thermal desorption-gas chromatography-
mass spectrometry/flame ionization detection; TD-GC-MS/FID), recent studies (Haeri-Ardakani et al., 2015; Jiang et al.,
2015) have shown that a significant portion of the S1 peak might be due to contamination, originating from drilling additives.
This impact can become particularly important when oil-based muds are used for drilling. For a sample from the Montney
Formation (Alberta, Canada), Jiang et al. (2015) indicated recently that the S1 peak was mainly composed of drilling mud
additives (nC14 alkene and diesel) associated with mud invasion during coring. Those authors also showed that more than
18% of the S1 peak for a sample from the Nordegg Formation (Alberta, Canada) was generated due to the contamination.
Haeri-Ardakani et al. (2015) reported further that while the comparatively high S1 values from shallower depth of the Utica
shale were indication of the present of light hydrocarbons (composed of C9 to C22 alkanes), the comparatively lower S1
values from deeper wells mostly originated from drilling additive contamination (composed almost entirely of C8 alkenes;
oil-based drilling mud). The mud used for drilling of the well associated with batch A was an oil-based mud (invert drill).
The contributions of light hydrocarbons and contamination to the low S1 peaks obtained for these samples is therefore not yet
clear. Additional TD-GC-MS/FID tests are necessary to quantify the ratios between the light hydrocarbons and contamination
in these samples.

Impact of solvent-extraction on grain density, pore volume attributes and permeability. The impact of toluene-extraction
on grain density of Montney samples depends on the organic matter content and other sample-to-sample variations (Fig. 7a).
For batch A, except for two samples (#2A, #3A), the grain density values measured after toluene-extraction are larger than
those measured in the “as-received” condition. The two samples that do not follow this trend (#2A, #3A) have low TOC
contents (Table 2). In contrast to batch A, for all samples from batch B, the grain density values measured after toluene-
extraction are larger than those measured in “as-received” state (Fig. 5). This observation is generally expected as toluene-
extraction results in (partial) removal of oil and solid bitumen from the pore network of the samples, and consequently, grain
density increases. The impact of methanol-extraction on grain density values of the Montney samples is variable (Fig. 7a).
For batch A, except for one sample (#10A), the grain density values measured after methanol-extraction are unexpectedly
smaller than those measured after toluene-extraction. Except for two samples (#7A, #10A), the methanol-extracted grain
density values for batch A are even smaller than those measured in the “as-received” state. In contrast to batch A, for all
samples from batch B, the grain density values measured after methanol-extraction are consistently larger than those
measured in the “as-received” state and after toluene-extraction (Fig. 5).
The impact of toluene-extraction on permeability of Montney samples also appears to be dependent on the organic
matter content (Fig. 7b). For batch A, six of the ten samples have crushed-rock permeability values that are larger after
toluene-extraction than those measured in the “as-received” condition. Three (#2A, #3A, #12A) out of four samples that do
not follow this trend have comparatively low TOC contents (Table 2). In contrast to batch A, for all samples from batch B,
the crushed-rock permeability values measured after toluene-extraction are consistently larger than those measured in the “as-
received” state (Fig. 6). Similar to grain density analyses, the impact of methanol-extraction on crushed-rock permeability
values of Montney samples is variable (Fig. 7b). For batch A, except for two samples (#7A, #10A), the crushed-rock
permeability values measured after methanol-extraction are unexpectedly smaller than those measured after toluene-
extraction. For half of the samples, the permeability values measured after methanol-extraction are even smaller than those
SPE-175954-MS 9

measured in the “as-received” state. In contrast to batch A, for all samples from batch B, the crushed-rock permeability
values measured after methanol-extraction are consistently larger than those measured in the “as-received” state and after
toluene-extraction (Fig. 6).

Fig. 7 — Impact of original (as-received) TOC content on the evolution of grain density and permeability after solvent-extraction.
In contrast to some of the unexpected results obtained from grain density and crushed-rock permeability analyses for
batch A, the low-pressure gas (CO2, N2) adsorption data indicate that specific surface areas and pore volumes increase
consistently with sequential solvent-extraction (Figs. 3-4; Fig. 8). These data further support the idea that the percentage of
micro-, meso- and macropores increases significantly after sequential solvent-extraction with toluene and methanol. The
increase of specific surface area and pore volume after solvent-extraction is more significant for samples with higher TOC
content (Figs. 3-4; Fig. 8). This result is expected because the removal of hydrocarbons, solid bitumen and salt from the pore
network would increase the surface area and allow access to previously occluded pores, thereby increasing pore volume.
Previous studies (Wei et al., 2014; Furmann et al., 2013; Milliken et al., 2013; Valenza et al., 2013) reported an increase in
surface area of shale samples after solvent-extraction, most significantly for samples within a vitrinite reflectance range of 1 –
1.5%. These studies attributed the increase in surface area to the opening of previously bitumen-clogged pores after solvent-
extraction.

Fig. 8 — Impact of original (as-received) TOC content on the evolution of surface area after solvent-extraction.

Due to logistics-related issues, unfortunately, no Rock-Eval data was collected for samples from batch B. Therefore,
the TOC contents (as well as other Rock-Eval parameters) are not available for these samples. However, the TOC contents of
samples from batch B are generally expected to be higher than those from batch A. For three samples from the same well and
depth interval as those of batch B, the TOC contents (based on LECO method) range between 1.2 and 1.4 wt. %. Therefore,
we hypothesize that the progressive increase of grain density and permeability with sequential solvent-extraction for batch B
is due to comparatively larger dissolution of organic matter from the pore network of these samples. The collection of TOC
data for this sample suit is necessary to confirm this hypothesis.
SPE-175954-MS 10

As previously noted, solvent-extraction with methanol (or chloroform-methanol) is routinely performed to remove
salts precipitated in the pore network of samples after the Dean-Stark distillation process with toluene and/or sample
uplift/drying during core retrieval. The density values of the precipitated salts (on average, 2.17 g/cm3) are dependent on their
composition, however, are generally expected to be smaller than other dominant minerals in the samples (on average, 2.6
g/cm3). The precipitated salt in the rock matrix could therefore potentially decrease grain density to some extent after toluene-
extraction. These residual salt compounds may also cause blockage of a portion of the pore throats in the rock matrix after
toluene-extraction. It is therefore expected that the removal of these precipitated salt compounds (methanol-extraction) results
in an increase in grain density and permeability. Nevertheless, experimental data obtained for batch A, as opposed to batch B,
unexpectedly indicates that grain density and permeability values measured after methanol-extraction are generally lower
than those measured after toluene-extraction. The reason(s) for this decline is not yet clear to us. It is possible that the
repeated extraction and drying of the samples with solvents resulted in some unknown phenomena that cause these
unexpected results.
While these unexpected results are yet to be fully explained, there are a number of hypotheses which could be used
to explain the differences observed between the two datasets (batch A and batch B): (1) inefficient/incomplete solvent-
extraction and/or drying of the samples from batch A, (2) different degrees of salt precipitation after toluene-extraction and/or
sample uplift/drying during core retrieval for batches A and B, and (3) experimental/analytical uncertainties and errors.
Further discussion of these hypotheses is provided in the following sections.
The efficiency of solvent-extraction and drying processes. It could be argued that incomplete/inefficient solvent-extraction
might have contributed to the unexpected results observed for batch A. The abundance and distribution of chemical
functional groups in toluene- and methanol-extracts can be potentially identified using Fourier transform infrared (FTIR)
spectroscopy (Wei et la., 2014). These data were not collected in this study. Therefore, the efficiency of solvent-extraction
processes cannot be determined from the composition of solvent-extracts. Nevertheless, the almost complete removal of
organic matter after toluene/methanol extractions (Table 4) provides relative confidence that the solvent-extraction procedure
is complete. Further, as previously noted, the solvent-extraction and drying processes were undertaken for a longer time (10
days) than routine “best practice” procedure (7 days). Based on these observations/precautions, the incomplete/inefficient
solvent-extraction is not expected to contribute to the unexpected results.
It could be further argued that inefficient/incomplete drying of the samples after solvent-extraction might have
contributed to the unexpected results obtained after solvent-extraction for batch A. Careful gravimetric recording of the
sample weights after solvent-extraction and during the drying process was carried out to ensure satisfactory evaporation of
the solvents. Helium pycnometry and crushed-rock permeability tests were performed only after the mass of the samples was
constant. Nevertheless, after obtaining some of the unexpected results, a set of complementary analyses were performed
consisting of the re-drying of the samples in the oven and continuous measurements of the mass of the samples. Fig. 9
indicates that variation in the mass of the samples is relatively minor (± 0.1%) during the re-drying procedure for toluene-
and methanol-extracts.

Fig. 9 — Variation in mass of five selected samples from batch A during the re-drying analysis.

Further, for toluene-extracted samples, Fig. 10 indicates that the variation in grain density values re-measured
during the re-drying process is minor (maximum ± 0.005 g/cm3). Based on these observations/precautions, the
incomplete/inefficient drying process is also not expected to contribute to the unexpected results.
SPE-175954-MS 11

Fig. 10 — Variation in grain density values of five selected samples from batch A during the re-drying analysis.

The impact of salt precipitation and formation water salinity. It could be argued that some of the differences observed
between batches A and B after methanol-extraction may be due to the different degrees of salt precipitation in these samples
after sample uplift/drying during core retrieval. The precipitation of salt in the rock samples is dependent on the “in-situ”
water/brine content and the salinity of the “in-situ” (formation) water. Wood (2013) reported that while water saturations
(bulk volume water) in Lower Montney are generally less than 1%, the water saturations in Upper Montney commonly rang
between 1 and 3%. Wood (2013) further reported that, while there is no significant interrelationship between water saturation
and porosity in Lower Montney, the water saturation in Upper Montney increases with increasing porosity. As highlighted by
Wood (2013, 2015), these data indicate that, compared to the Upper Montney, the Lower Montney is most likely at
irreducible water saturation. The samples from batch A belong to Lower Montney, and therefore, the “in-situ” water content
is expected to be relatively small for these samples.
The salinity of the “in-situ” (formation) water is another factor which controls the degree of salt precipitation in the
matrix of rock after sample uplift/drying during core retrieval. The salinity of formation water in the Montney ranges
generally between 150,000 to 300,000 ppm (Wood, 2013, 2015). Michael and Bachu (2002) analyzed the chemistry of
formation water in the Mississippian-Jurassic succession in the west central part of the Alberta Basin (Canada) using the
publicity available data. Michael and Bachu (2002) suggested that the salinity of formation water increases northwestwards
from about 50 to about 150,000 ppm. These data are related to a specific area (western Alberta, eastern British Columbia)
and cannot be easily related to other areas in the Montney. Nevertheless, the northwest increase of formation water salinity in
Alberta might be an indication that the salinity of formation water becomes greater in northeastern British Columbia.
Presumably, the higher salinity of formation water for batch B results in a higher content of precipitated salts after sample
uplift/drying during core retrieval. Under these circumstances, the impact of methanol-extraction on grain density and
permeability is expected to be more significant for batch B (northeastern British Columbia) compared to batch A (western
Alberta). However, because there is no “in-situ” water content/salinity data available for batches A and B, this mechanism
cannot be confirmed at this time.
The uncertainties in bulk/grain density, low-pressure gas adsorption and crushed-rock permeability analyses. A
comparison of the different petrophysical properties after the various sample treatments is not complete without discussing
the potential sources of uncertainty/error in experimental/evaluation procedures. This is of particular importance for
unconventional reservoirs, which commonly have low to extremely-low porosity and permeability values. The errors in
bulk/grain density measurements may only have a minimal effect on the porosity values estimated for conventional reservoirs
(common porosity range: 15-30%) but could significantly affect the porosity values estimated for unconventional reservoirs
(common porosity range: 2-10%). Simple calculations confirm that, in this lower range of porosity (2-10%), a measurement
error of 0.01 g/cm3 in bulk and/or grain density could create errors up to 0.5 units in the estimated porosity values. The error
in porosity values in turn affects the estimated crushed-rock permeability values as porosity is one of the inputs for
evaluation/interpretation of pressure transient curves obtained from crushed-rock permeability tests.
In this study, the impact of different possible sources of uncertainty on grain density and crushed-rock permeability
measurements was determined by performing repeat tests. These repetitive measurements verified (1) the impact of sample
cell volume on measured grain density values and (2) the influence of the test duration, pre-pressurizing of the sample cell
SPE-175954-MS 12

(the evacuation status of the sample), and operator’s bias on measurement and evaluation of crushed-rock permeability
values. Three sample cells with different volumes (10 cm3, 35 cm3, 100 cm3) were used in helium pycnometry tests to
investigate the effect of sample cell volume on the grain density outcomes. The crushed-rock permeability tests were repeated
on identical samples using different test durations with and without pre-pressurizing. The evaluation of permeability in
crushed-rock technique might be partly dependent on the operator’s judgment/choice of which part/interval of the pressure
transient curve should be chosen for calculation/modeling of the permeability. Therefore, identical pressure transient curves
obtained during crushed-rock permeability tests on identical samples were randomly selected and evaluated by two different
operators to determine the sensitivity of the crushed-rock permeability measurements to the operator bias.
The results of these repetitive measurements indicate that the uncertainty associated with the use of different sample
cells is less than 0.005 g/cm3 in helium pycnometry tests (Fig. 11a). Interestingly, the grain density values measured with the
medium size sample cell (35 cm3) appear to be smaller than those measured with the small and large sample cells (except for
sample #7A). It should be noted that the volume of all sample cells were calibrated before each grain volume/density test.
Therefore, the uncalibrated volume of the medium size sample cell might not be the reason for this discrepancy. It is further
recommended that the sample volume should not be less than 10% of the sample cell volume in helium pycnometry tests (due
to signal-to-noise ratio) – the smaller the void volume (difference between sample cell and sample volumes), the less the
error associated with the measured grain volumes/densities. In this study, all sample cells were filled with as much crushed-
rock sample as possible before performing the helium pycnometry tests. Therefore, this factor also might not account for the
observed discrepancy. The effect of sample cell size continues to be investigated.
The results of these repetitive measurements further indicate that the uncertainty originating from the duration of
tests and evacuation status of the sample (with and without pre-pressurizing) can be as large as 50% of the
measured/evaluated value in crushed-rock permeability tests (Figs. 11b-c). The uncertainty associated with the operator’s
bias is less than 5% of the measured/evaluated crushed-rock permeability value (Fig. 11d). Based on repeated measurements,
conservative uncertainties (maximum variation) are provided for grain density, porosity and permeability measurements.
These uncertainties (error bars) are incorporated in the results shown for the different tests/states.

Fig. 11 — Effects of different controlling factors on uncertainty of helium pycnometry and crushed-rock permeability tests.
SPE-175954-MS 13

The crushed-rock permeability technique is the most recent, and the least developed methodology for measurement
of permeability in unconventional reservoirs. This technique is comparatively simple and fast, however, there are still
ongoing debates about its theoretical and experimental principles. In addition to the variation in designs and experimental
operation (vacuum, temperature-controlled bath, etc), currently, different laboratories are using different
physical/mathematical formulations/models to evaluate the pressure transient data obtained from the experiment to
calculate/estimate the permeability values. The application of different formulations/models is probably one of the main
reasons that the crushed-rock permeability values obtained by different laboratories are not comparable. Principally, the
pressure transient data can be evaluated using both pressure-driven volumetric flow (permeability; Darcy equation) and
diffusivity flow regimes (due to very low flow rates). Using the pressure-driven volumetric flow regime (permeability; Darcy
equation), it is further possible to include or exclude the non-Darcy flow effect (Klinkenberg effect) in the mathematical
formulation. Besides these experimental/modeling discrepancies, there are other important parameters such as particle size,
particle shape and sample preparation procedures which can significantly affect the outcome of these tests. As has been
highlighted by other research groups (Heller et al., 2014; Sinha et al., 2012; Sondergeld et al., 2010), there is a need for
establishing measurement and data evaluation standards for this permeability technique. Our research group is currently
developing different physical/mathematical models for evaluation of the pressure transient data in crushed-rock permeability
tests (Haghshenas et al., 2015). Using different physical/mathematical models, it is then possible to examine the impact of
different evaluation techniques on the crushed-rock permeability results. These results will be reported in future publications.
It should be noted that grain density and permeability values measured for batch A span a smaller range compared
to batch B (Figs. 5-6). Therefore, the impact of experimental uncertainties/errors on grain density and permeability values
measured for batch A is expected to be more significant compared to batch B. Considering the experimental errors, there is
an overlap between grain density and permeability values measured in three states of treatment for batch A (Figs. 5-6).
Therefore, the unexpected grain density and permeability results observed for batch A are partly attributed to the
experimental uncertainties/errors. Further experimental investigations are, nevertheless, essential to interpret some of the
unexpected outcomes observed in this study.

Implications of the Experimental Results for Tight Oil/Gas Reservoirs. The hydrocarbon storage and transport properties
of tight oil and liquid-rich gas reservoirs depend on porosity, pore size distribution and permeability. Knowledge of these
petrophysical properties with and without the presence of solid bitumen can potentially aid in a better prediction of
hydrocarbon content, reduction of exploration risk and mitigation of resource estimation and production uncertainties. For the
Montney Formation, as a world-class tight oil and liquid-rich gas reservoir, the comparison of petrophysical characteristics
before and after solid bitumen and salt removals reveal a variety of interesting results. For some samples, there is little
noticeable change in porosity and permeability after sequential removal of solid bitumen and salts from the pore network,
while for some other samples porosity and permeability increase progressively with sequential solvent-extraction with
organic solvents (Fig. 12).

Fig. 12 — The impact of sequential solvent-extraction on porosity and permeability of the Montney Formation. rp35 calculations were
performed using the approach of Aguilera (2002).

These comparative datasets collected on “as-received” and solvent-extracted samples constrain the evolution of
fluid storage and transport properties of the Montney Formation during hydrocarbon charging. At this time, due to the
lack of experimental data, it is not possible to be more predictive about the samples that possibly experience a more
significant increase in porosity and permeability after solvent-extraction. Further systematic experimental examinations
SPE-175954-MS 14

are necessary to investigate the impact of rock type (mineralogical composition) and burial/diagenetic history on the
presence of pore-blocking materials and the efficiency of their removal using organic solvents. Nevertheless, these
comparative datasets highlight that the design of stimulation treatments can potentially be optimized for different
intervals. This optimization may include adding fluid additives in the hydraulic fracturing fluid to enhance bitumen
removal, and therefore, induce porosity and permeability enhancement.
Most operators in Montney believe that there is no solid halite in-situ in the reservoir. The presence of
hypersaline water in the Montney could, however, potentially cause salt precipitation after core retrieval, decreasing
porosity and permeability obtained from routine core analysis. The Dean-Stark extraction with methanol could possibly
remove the precipitated salt, mitigating this phenomenon. However, it should be noted that the induced pore volume after
salt removal is expected to be occupied by hypersaline water in the subsurface. The hypersaline formation water in the
Montney exists as free, or more commonly, clay-bound water, creating a continuous pathway for electrical conductivity,
as confirmed by Wood (2013, 2015) using correlations between deep resistivity (from logs) and bulk volume water
(BVW; obtained from full-diameter cores). This correlation breaks down only in regions with porosity less than about
1.5%. Most Montney zones with well-connected hypersaline water exhibit progressive increases in salinity of the flow-
back water with time after hydraulic fracturing.

Conclusions
In a recent study (Ghanizadeh et al., 2015), the petrophysical and geomechanical characteristics of a selected sample suite
from Montney Fromation were examined in the “as-received” condition. The present study is a continuation of the previous
work, aiming to elucidate the influence of solvent-extraction on geochemical and petrophysical characteristics of the
Montney Formation. The following conclusions can be drawn from the present work:

 Rock-Eval data indicate that there is a significant loss of the S2 component after solvent-extraction with toluene and
methanol. This significant loss of the S2 peak is attributed to the removal of solid bitumen from the pore network of
the samples. Compared to the “as-received” state, the toluene-extraction results in organic matter removals, ranging
between 29 and 76%. The methanol-extraction almost completes the extraction of organic matter, ranging between
87 and 100%.
 The impact of solvent-extraction on grain density, pore network attributes and permeability of Montney appears to
be dependent on the organic matter content and other sample-to-sample variations. While for one dataset (batch A),
the evolution of these petrophysical properties is variable, for the other dataset (batch B), grain density, pore
network attributes and permeability increase systematically after sequential solvent-extraction with toluene and
methanol.
 The variable outcomes for one of the datasets (batch A) are possibly attributed to (1) different degrees of salt
precipitation after toluene-extraction and/or samples uplift/drying during core retrieval and/or (2) associated
experimental uncertainties/errors. A detailed discussion of experimental uncertainties/errors was provided to
elucidate the impact of the experimental uncertainties/errors on the outcomes. Further experimental investigations
are, nevertheless, essential to interpret some of the unexpected outcomes observed in this study.

Acknowledgements
The core and financial support for this study was provided by Seven Generations Energy Ltd and Black Swan Energy Ltd.
We gratefully acknowledge this ongoing support. The authors also thank the management of both companies for giving
permission to present and publish this material. Bob Teichrob (Seven Generations Energy Ltd), Glen Nevokshonoff (Seven
Generations Energy Ltd), Robert Riopel (Seven Generations Energy Ltd), Heather Gray (Black Swan Energy Ltd), Jon
LaMothe (Black Swan Energy Ltd), Federico F. Krause (University of Calgary), and Per Pedersen (University of Calgary)
are thanked for their fruitful comments and interesting discussions. The SMP-200 permeameter used in this study was
purchased and installed at the University of Calgary using a Canadian Foundation for Innovation - Leaders Opportunity Fund
grant (+Alberta provincial match, Alberta Advanced Education and Technology (AAET) - Small Equipment Grant) to
Clarkson. Amin Ghanizadeh thanks University of Calgary for the “Eyes High” Postdoctoral Fellowship (University of
Calgary). Partial funding for Ghanizadeh was also provided by an NSERC Discovery grant to Clarkson. The authors also
gratefully thank the sponsors of the Tight Oil Consortium hosted at the University of Calgary.

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