Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142

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Journal of Unconventional Oil and Gas Resources

journal homepage: www.elsevier.com/locate/juogr

Porosity and pore size distribution of deeply-buried fine-grained rocks:

Influence of diagenetic and metamorphic processes on shale reservoir
quality and exploration
Gareth R.L. Chalmers ⇑, R. Marc Bustin
Earth and Ocean Sciences, University of British Columbia, Vancouver, B.C. V6T 1Z4, Canada

a r t i c l e i n f o a b s t r a c t

Article history: Significant exploration risks are associated with the pursuit of deeply-buried shale gas reservoirs due to
Received 5 August 2014 pore volume reduction and changes in pore size distribution. These changes in pore character result in
Revised 9 August 2015 decreases in gas in place and permeability. A suite of shale, low grade, pelitic metamorphic and a granite
Accepted 24 September 2015
outcrop samples from various location in North America have been selected to span the later stages of
Available online 19 October 2015
diagenetic, epimetamorphic (epizone) and anchimetamorphic (anchizone) processes to evaluate the
changes in the inorganic pore volumes and size distributions. Diagenetic/metamorphic ranking of
Keywords:
samples were determined by the illite crystallinity method. Pore volumes reduce with increasing
Pore size distribution
Metamorphic processes
maturity/metamorphic grade. The loss of mesopore volume (2–50 nm) with increasing maturity is the
Porosity cut-off cause of the reduction in porosity. The reduction in mesopore volume is interpreted to be due to the
Mesopore volumes authigenic recrystallization and growth of the clay minerals. As maturity/metamorphic grade increases
there is a relative increase in the macropore (>50 nm) and micropore (<2 nm) size fractions. The increase
in micropore volumes may be attributed to the development of secondary porosity within the kerogen. At
higher maturity/metamorphic grade (i.e., illite crystallinity < 0.2 D2h) porosity values range between
0.9% and 3.6% indicating that fracture porosity is not the only mechanism of gas storage in deeply buried
shale (and pelitic metamorphic rocks) reservoirs. Matrix porosities in these higher maturity/metamor-
phic samples are comparable to matrix porosities of the Horn River shales of British Columbia and other
shale reservoirs. Similar to the Horn River and Doig–Montney shales, the reduction in mesopore volumes
may reduce the matrix permeability of these rocks and fracture stimulation will be an integral
component of the completions program to access hydrocarbons.
Ó 2015 Elsevier Ltd. All rights reserved.

Introduction porosity. Porosity is a significant control on gas-in-place estima-

As global exploration of shale gas intensifies there is significant
risk associated with the pursuit of shale gas resources that are dee-
ply buried (i.e., Haynesville Formation, Mississippi, USA; Mainland
Resource Inc., 2009) due to diagenetic and metamorphic processes
that reduce porosity, alter pore size distributions and reduce
permeability. The decrease in porosity with increasing maturity
within sandstones and shales is well documented within the oil
and gas windows (i.e., vitrinite reflectance – Ro 0.5–2.0%, Hunt,
1995; Schimmelmann et al., 2006). The change in pore characteris-
tics results in lower gas capacity and hence lower permeabilities
(Biryukov and Kuchuk, 2012). Porosity, as described in this study,
refers to the total matrix porosity (i.e., Sw = 0) and excludes fracture
⇑ Corresponding author.
E-mail address: garethchalmers@gmail.com (G.R.L. Chalmers).
tions for shale gas resources as illustrated for the regional evalua-
tion of the Jurassic Gordondale Member (Ross and Bustin, 2007),
Devonian Horn River strata (Ross and Bustin, 2007), Cretaceous
Buckinghorse Formation (Chalmers and Bustin, 2008a) and the
Cretaceous Shaftesbury Formation (Chalmers and Bustin, 2012a)
in northeastern British Columbia. A positive relationship exists
between porosity and total gas (free + sorbed gas) capacity of a
shale reservoir (Chalmers and Bustin, 2008a; Appendix F). The free
gas component increases relative to the sorbed gas component in
deeply buried shales because of reservoir temperature increases
with depth of burial. Sorbed gas is an exothermic reaction and an
increase in temperature will reduce the volume of sorbed gas
and increase the free gas content of a reservoir (Ross and Bustin,
2008) and majority of the free gas content will reside in the
inorganic pore system. For example, areas that experience high
geothermal gradients (i.e., Horn River Basin, British Columbia),

http://dx.doi.org/10.1016/j.juogr.2015.09.005
2213-3976/Ó 2015 Elsevier Ltd. All rights reserved.
 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142
the free gas component is a significant portion of gas-in-place (GIP)
estimates for gas shale resources (Ross and Bustin, 2008) and any
loss of porosity associated with increased burial and associated
chemical and mechanical alteration (Foscolos, 1990; Kisch, 1991;
Kubler and Jaboyedoff, 2000) may significantly reduce the gas-
in-place estimation of the reservoir. Requirements for economic
production (i.e., permeability, drainage volumes, fracability) and
gas-in-place estimations are dependent on effective porosity and
the pore size distribution (PSD) of the reservoir and interconnectiv-
ity of the pore system. The evaluation of the PSD is fundamental in
the understanding of a shale gas reservoir capacity and permeabil-
ity as the PSD is a control on matrix permeability of shale reser-
voirs. Studies have shown that higher matrix permeabilities in
both the Horn River (Chalmers et al., 2012b) and Triassic
Doig–Montney (Chalmers and Bustin, 2012b) shales exhibit a bal-
anced ratio between micro-, meso- and macroporosity compared
to lower permeability shales. To adequately describe the PSD of
fine-grained reservoirs, the IUPAC (1994) classification system
which was developed for porous solids has been adopted for this
study, as the majority of pore throats in shale reservoir pore
systems are within the nanometre scale (Chalmers et al., 2012a;
Milliken et al., 2013). In the IUPAC classification micropores are
<2 nm, mesopores between 2 and 50 nm and macropores are
>50 nm (Rouquerol et al., 1994). Shale pore classification system
by electron microcopy (i.e., Loucks et al., 2012) do not include
pores that are below 5–8 nm which are a significant portion of
the total porosity of a shale reservoir (Chalmers et al., 2012a;
Milliken et al., 2013; Mastalerz et al., 2013). Hence, electron micro-
scopy does not capture changes that occur within the nanometre
scale since all pores are described as ‘‘nanopores”. A study of pore
volumes using electron microscopy indicates that this technique is
unable to quantify up to 98% of the total porosity of shale reservoir
(Milliken et al., 2013). Gas adsorption and mercury porosimetry
analyses and description of the pore size distribution using the
IUPAC classification system have been successfully used to identify
changes in PSD with parameters like maturity (Chalmers and
Bustin, 2012a; Mastalerz et al., 2013), permeability (Chalmers
et al., 2012b) and with TOC content (Chalmers and Bustin,
2008b; Ross and Bustin, 2007, 2008; Tian et al., 2013) and have
been adopted for this investigation.
This study will evaluate the relationship between maturity,
porosity and PSD to include maturities greater than 2.0% Ro to
the point of incipient metamorphism (epimetamorphism; Kisch,
1991; Kubler and Jaboyedoff, 2000) as past similar studies have
limited their investigation to maturities below 2.0% Ro. The
inorganic pore volume and PSD of a suite of shales and pelitic
metamorphic rocks are investigated to gain an understanding of
the effect of diagenesis and metamorphic processes have on poten-
tial shale gas reservoirs within the dry thermogenic gas window
(Ro > 2%; Schimmelmann et al., 2006) and into the anchizone and
epizone. The organic pore volume is not considered in this study
as samples are overmature resulting in kerogen that is inert resid-
ual carbon and no changes to the organic porosity are expected.
Methodology
We have analysed a suite of samples from various locations in
North America (Fig. 1; Table 1) that span a range of diagenetic to
metamorphic processes to understand the changes in the PSD
and porosity that are associated with the inorganic content (TOC
lean rocks; <1.5 wt%). Majority of samples in this study do not
represent a producing reservoir as no producing reservoirs have
experienced maturities above 2.0% Ro, therefore these samples
are being used in the study to investigate how the inorganic pore
system changes with diagenetic and metamorphic processes.
135
Matrix permeability will also be affected by these changes but is
not in the scope of this study. A granite sample is included in the
suite of rocks to evaluate the porosity and PSD as fractured igneous
rocks, like metamorphic rocks are also considered to have no
matrix porosity (Biryukov and Kuchuk, 2012) with hydrocarbon
production considered to be exclusively from fracture networks
(i.e., Yemen; Legrand et al., 2011). The criteria for selection are
based on: (1) pelitic origin; (2) TOC lean; and (3) span diagenetic
to metamorphic processes.
X-ray diffraction and Rietveld analysis
Seventeen crushed samples (<250 lm) were mixed with etha-
nol, hand ground in a mortar and pestle and then smear mounted
on glass slides for X-ray diffraction analysis. A normal-focus Cobalt
X-ray tube was used on a SiemensÒ Diffraktometer D5000 at 40 kV
and 40 mA. The mineral composition was semi-quantified by
Rietveld analysis (Rietveld, 1967) using Bruker AXS TopasÒ V3.0
software.
Illite crystallinity
A number of well-established analytical techniques measure
the level of diagenesis and metamorphism of sedimentary rocks.
The degree of diagenesis/metamorphism is measured on the
organic component (i.e., vitrinite reflectance, Tmax, proximate
analysis; Diessel, 1992; Taylor et al., 1998) or on the mineral
matter (i.e., illite crystallinity; Kubler, 1968; Kisch, 1974, 1980,
1991; Kubler and Jaboyedoff, 2000). Illite crystallinity is a reliable
method to determine maturity or metamorphic grade for sedimen-
tary and pelitic low grade metamorphic rocks in late stages of dia-
genesis and incipient metamorphism (Foscolos, 1990; Kisch, 1991;
Kubler and Jaboyedoff, 2000). Metamorphic zone boundaries are
defined by changes in mineral assemblages and begin at the end
of dry gas generation which is termed the anchizone (Kisch,
1991). The greenschist facies minerals (i.e., chloritoids) define
rocks within the epizone and the transformation of dickite to pyro-
phyllite (Kubler, 1967). Illite crystallinity is a reliable measure of
diagenetic and metamorphic processes as the growth and recrys-
tallization of illite, in particular, the increase in the thickness of
the illite crystallites occurs with increasing metamorphic grade
in sedimentary rocks (Abad, 2007; Meunier, 2005). This study
has utilised illite crystallinity method (Kubler, 1968) as a measure
of maturity for this suite of samples as this is most reliable method
for overmature TOC-lean rocks. Illite crystallinity is favoured for
fine-grained sedimentary rock that may lack the size and quantity
of dispersed organic matter to provide valid vitrinite reflectance
measurements and the S2 is too depleted for Tmax values from
programmed pyrolysis (Peters, 1986). S2 peak is the second peak
in rock–eval pyrolysis that represents the hydrocarbon generative
potential of the sample and this peak is used to determine the Tmax
and maturity of the rock (Espitalie et al., 1985). Samples used in
this study are TOC lean (<1.5 wt%) and vitrinite and rock–eval
pyrolysis cannot provide valid results to measure their maturity.
The thickness of illite crystallites is measured by the peakedness
of the first basal reflection (0 0 1) peak at X-ray diffraction spacing
of 10 angstroms and reported as a peak width in degrees
(Blenkinsop, 1988; Kisch, 1991; Abad, 2007). The boundary
between diagenesis and the initiation of metamorphism (anchi-
zone) is considered at 0.42° D2h illite peak and the boundary
between anchizone and epizone at 0.25° D2h illite peak (Kisch,
1991).
Protocols that have been developed to obtain consistent results
between laboratories (Kisch, 1991) have been implemented in this
study. Samples were disintegrated using mortar and pestle and
agitated by sonic bath in a distilled water and deflocculant
136 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142

Fig. 1. Locations of samples in British Columbia and Alberta, Canada (A) and in Vermont and New York, U.S.A. (B). Table 1 shows the group, formation and lithology of these
samples. Diagram modified from Acton et al. (2000), Coleman (1988), Desjardins et al. (2010), Fyles (1967), Hatch et al. (1988), Ruks et al. (2010) and Sullivan et al. (2012).
 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142 137

Table 1
The locality, stratigraphy and age of samples.

Sample ID Locality Group Formation Age Lithology

d-51-f-3iso Fort Nelson, BC, Canada Fort St John Garbutt Cretaceous Shale
14-20-77-3 Fort St John, BC, Canada Fort St John Moosebar Cretaceous Shale
d-75-e-6iso Fort Nelson, BC, Canada Fort St John Garbutt Cretaceous Shale
1331-1 Liard River, BC, Canada n/a Besa River Devonian Shale
11-7-16 Dawson Creek, BC, Canada Daiber Doig Triassic Shale
b-90-j-c3 Liard River, BC, Canada n/a Muskwa Devonian Shale
P1648 Lillooet, BC, Canada Lillooet n/a Lower Cretaceous Argillite
P95 Ainsworth, BC, Canada Milford n/a Carboniferous Pyritiferous Slate
P428 Louise Station, AB, Canada Gog Lake Louise Lower Cambrian Metargillite
P2525 Ainsworth, BC, Canada Milford n/a Carboniferous Argillite
P289 Mt. Morrisey, BC, Canada Nicola n/a Triassic Shale
P747 Gerald Island, BC, Canada Sicker n/a Permian argillite
P811 Gerald Island, BC, Canada Sicker n/a Permian Varved sediments
SS-3 Vancouver Island, BC, Canada Sicker n/a Permian Granite
SS-2 Lillooet, BC, Canada Lillooet n/a Lower Cretaceous Phyllite
P3687 Littleton, VT, USA n/a Littleton Devonian Phyllite
P431 Rochester, NY, USA Clinton Rochester Lower Silurian Green shale

(CalgonTM) mixture. To remove greater than 60 lm size fraction
clay-water-CalgonTM mixture was allowed to settle for less than
six hours and the top portion of the water column was siphoned
off. To obtain the grain size less than 2 lm size fraction, the
siphoned mixture is centrifuged at 600 rpm (Hathaway, 1956) for
2 min. The supernatant is decanted into clean centrifuge tubes
and 5–10 mL of 1 M CaCl2 (deflocculant) is added and agitated in
sonic bath. Mixture is then centrifuged at 2000 rpm for 5 min to
remove clay-sized sediment (less than 2 lm) from supernatant
(Issa et al., 2008). This remaining sediment was washed and cen-
trifuged with CaCl2 and then washed with distilled water to
remove excess CaCl2. Once the clay fraction is free of chloride ions
as determined by the silver nitrate test, 20 mL of distilled water is
added and agitated in ultrasonic bath and transferred by pipette to
XRD slides and allowed to dry in drierite-filled dissector. Only sam-
ples with greater than 3 mg/cm2 slide coverage are deemed accept-
able for XRD diffraction (Kisch, 1991).
Fine grained sedimentary rocks may contain degraded illite
illustrated by a broad XRD peak (Grim, 1968). The degraded struc-
ture is the result of either the loss of potassium due to alteration or
weathering of the illite (Holeman, 1965; Grim, 1968) in non-
marine conditions (McConchie and Lewis, 1980) or by chelation
of potassium ions by organic acids derived from the organic con-
stituents of the shale (McConchie and Lewis, 1980; Frey, 1988).
The degradation of illite will affect the illite crystallinity measure-
ment and erroneous interpretation of the level of diagenesis/meta-
morphism. The illite peak sharpens when the clays are saturated
with a KCl solution due to the addition of potassium ions into
the clay structure (Grim, 1968; McConchie and Lewis, 1980;
Howard, 1981). A 3 M KCl solution is used to saturate samples with
potassium ions if degraded illite is identified in a sample, prior to
XRD illite crystallinity analyses.
Porosity
Porosity is determined by mercury immersion (bulk density)
coupled with helium pycnometry (skeletal density; Lowell et al.,
2004). Samples (
30 g) are crushed between 20 and 30 mesh sizes
(841 and 595 micrometers) and dried at 110 °C to determine the
skeletal density by helium pycnometry at pressure < 25 PSI. The
total porosity is calculated from the difference between the bulk
and skeletal densities. All porosity measurements are on dried
samples (Sw = 0). Accuracy of bulk density measurements is less
than ±1% with repeatability of ±0.3%. Accuracy of skeletal density
measurements is ±2% with repeatability less than ±0.3%.
Pore size distribution (PSD)
PSD of gas shales is measured using both mercury porosimetry
(Webb, 2001) and low pressure gas adsorption analyses. Samples
are crushed (2–4 mm) and oven dried (110 °C), evacuated to
7E-07 MPa and intruded with mercury from 1E-05 to 431 MPa
using a MicromeriticsTM Autopore IV 9500 series apparatus. The
measured pressure range equates to the pore diameter range of
3–1.2  105 nm. The minimal pore diameter limit of 3 nm is within
the mesopore range and mercury porosimetry cannot detect
micropores within the pore system. Sample preparation includes
oven drying resulting in no water saturation. Samples crushed to
a uniform grain size are susceptible of containing void spaces
between crushed particles after mercury filling. These void spaces
may be included in the pore size distribution of the sample, partic-
ularly in the 10,000–100,000 nm size fraction creating erroneous
results. A large difference in the bulk density measurements from
mercury immersion and porosimeter will indicate that artificial
void spaces from sample preparation have been measured and
analyses is repeated until the difference is reduced to acceptable
levels (<5%).
Low pressure (<0.12 MPa) gas adsorption analyses using both N2
and CO2 probe gases have been used to measure the PSD between the
pore diameters of 0.35 and 300 nm (Quantachrome, 2008). Although
carbon dioxide is being used as the probe gas, the PSD limit of
0.35 nm is still relevant to methane (kinetic diameter of 0.38 nm).
Between 1 and 2 g of ground sample (<250 lm) is degassed at
70 °C for 12 h prior to analysis. Samples are crushed to <250 lm in
order to reach the vacuum threshold to begin the gas adsorption
analysis. The PSD will differ slightly between the two techniques
(porosimetry and gas adsorption analyses) due to sample prepara-
tion, analytical theory and calculations. CO2 adsorption is coupled
with the N2 adsorption analysis to examine the micropore size
fraction as the analytical temperature of N2 adsorption analyses is
too low (196 °C) for nitrogen molecules to access the fine microp-
ores (Unsworth et al., 1989). The analytical temperature used for CO2
adsorption analysis (0 °C) provides the necessary kinetic energy for
the CO2 molecule to access the micropores. Gas saturation curves are
cumulative gas adsorption plots (cm3/g) that is calculated from the
total CO2 and N2 pore volumes.
Samples were crushed for porosity and PSD analyses because:
(1) whole rock will take days instead of minutes to evacuate for
each analyses and therefore reduces analytical time and expense;
(2) porosity on crushed samples is standard industry practice due
to time constraints; and (3) whole rock shale samples may not
138 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142

have enough effective porosity volume in porosimetry to provide
an accurate result. If analyses were performed on whole rock the
porosity would be lower as not all pores would assessable as in
crushed rock samples.
Results
Whole rock mineralogy for the suite of 17 samples is shown in
Table 2. Quartz, illite/muscovite, kaolinite, chlorite, feldspar and cal-
cite components dominate the mineralogy with minor contributions
by pyrite, biotite, cordierite, dolomite and apatite. Illite/muscovite
content ranges between 1.9% and 48.2% and the quartz content
ranges between 15.2% and 65.7% (Table 2). Porosity, metamorphic
grade, average pore size and proportions of micro-, meso- and
macropore volumes for both gas adsorption and porosimetry are
shown in Table 3. The difference in the meso- and macropore
volumes between gas adsorption and porosimetry analyses are
due to the difference in measurement of pore size limits as
porosimeter cannot measure below 3 nm, the relative proportions
are only between meso- and macropores and does not include
micropore volumes.
A positive linear relationship exists between porosity and illite
crystallinity values (Fig. 2A). Porosity reduces with increasing
maturity/metamorphism for this suite of samples as increasing
illite crystallinity values indicate lower maturity (Fig. 2A; Table 3).
Loss of porosity is associated with the reduction in mesopore vol-
umes as illustrated by the positive relationship between the illite
crystallinity and the relative proportion of mesopores compared
to macropores (Fig. 2B; Table 3). The incremental pore volume dis-
tributions indicate the proportion of macropores remains similar
(particularly in the 10,000–100,000 nm size fraction) within
increasing maturity/metamorphism (Fig. 3). The similar pore vol-
umes in the 10,000–100,000 nm size fraction and the reduction
in mesopores with increasing maturity/metamorphism increases
the macropore volume proportion of the porosity (Fig. 2C). The
average pore size measured by N2 gas adsorption analyses
increases from 10 nm to over 30 nm (Table 3) with increasing
maturity/metamorphism highlighting the shift in PSD due to the
reduction in mesopores. Similar bulk density measurements from
mercury immersion and porosimeter (<3.3% difference) indicate
the incremental pore volumes between 10,000 and 100,000 nm
are not an artifact of measurement of void spaces that may occur
during the mercury filling of crushed, granular samples. The pro-
portion of micropores compared to meso- and macropore volumes,
increases with the increase in maturity and metamorphic grade
(Fig. 2D). PSD by gas adsorption illustrates this general trend of
increasing proportion of micropores with increasing illite crys-
tallinity (Fig. 4).
The outlier (cross symbol in Fig. 2A; Sample # P3687) within
the porosity–maturity/metamorphism plot is a phyllite and illus-

Table 2
Mineralogy derived from X-ray diffraction and Rietveld (semi-quantitative) analyses. Samples that contain paragonite are not used in this study.

Sample ID Quartz Illite/Muscovite Biotite Kaolinite Chlorite Pyrite Feldspar Calcite Dolomite Apatite Cordierite
d-51-f-3iso 37.5 30.7 0.0 8.9 2.4 1.3 19.3 0.0 0.0 0.0 0.0
14-20-77-3 43.6 32.1 0.0 1.9 3.7 0.0 18.6 0.0 0.0 0.0 0.0
d-75-e-6iso 24.0 72.1 0.0 2.9 0.0 0.0 0.6 0.0 0.0 0.0 0.0
P431 31.1 48.2 0.0 4.9 1.6 1.8 10.6 0.0 1.8 0.0 0.0
1331-1 42.4 8.0 0.0 0.0 0.3 2.1 7.5 26.4 13.2 0.0 0.0
11-7-16 27.9 8.9 0.0 0.0 0.0 1.8 14.8 23.1 17.2 2.9 0.0
b-90-j-c3 65.7 23.8 0.0 0.0 0.0 2.4 2.2 3.1 2.9 0.0 0.0
P1648 32.8 12.6 0.0 4.1 1.8 0.8 39.5 8.5 0.0 0.0 0.0
P95 40.9 27.9 0.0 0.1 1.0 1.9 12.0 0.0 16.2 0.0 0.0
P428 15.4 1.9 0.0 0.0 0.0 0.5 21.5 57.5 4.0 0.0 0.0
P2525 22.2 8.1 0.0 2.3 1.3 1.1 14.5 49.2 1.5 0.0 0.0
P289 40.1 13.7 0.0 3.9 17.7 0.2 22.5 0.0 2.1 0.0 0.0
P747 15.2 24.7 0.0 6.5 20.7 0.7 30.5 1.8 0.0 0.0 0.0
P811 30.9 10.6 0.0 9.7 0.1 0.0 47.3 1.0 0.0 0.0 0.0
SS-3 34.3 4.0 4.4 2.3 1.4 0.0 53.7 0.0 0.0 0.0 0.0
SS-2 6.1 3.8 12.4 2.6 3.4 0.0 66.4 0.0 0.0 0.0 5.4
P3687 44.4 4.0 13.2 1.1 1.2 0.0 36.2 0.0 0.0 0.0 0.0

Table 3
Rock type, porosity, illite crystallinity, metamorphic zones, average pore size from N2 adsorption analyses, pore size distribution from gas adsorption and porosimetry analyses.

Sample Porosity Illite Low grade Average CO2 total Gas adsorption Gas adsorption Gas adsorption Porosimetry Porosimetry
number (%) crystallinity metamorphic pore size volume. (%) micropore (%) mesopore (%) macropore mesopore macropore
(° D2h) zones (nm) (cc/100 g) volume volume volume volume (%) volume (%)
d-51-f-3 9.54 1.08 Diagenesis 11.12 0.80 24 63 13 83 17
14-20-77-3 5.49 0.96 Diagenesis 15.01 0.23 36 49 15 76 24
d-75-e-6 6.47 0.88 Diagenesis 8.30 0.24 35 55 10 70 30
P431 5.28 0.68 Diagenesis 11.33 0.26 55 35 10 41 59
1331-1 2.08 0.5 Diagenesis 21.86 0.10 41 42 17 27 73
11-7-16 2.35 0.33 Anchizone 58.54 0.08 60 18 22 19 81
b-90-j-c3 3.90 0.33 Anchizone 25.08 0.36 48 22 30 27 73
P1648 2.11 0.25 Anchizone 31.76 0.13 58 21 21 12 88
P95 1.94 0.23 Epizone 47.08 0.12 60 19 21 31 69
P428 2.16 0.2 Epizone 36.68 0.09 – – – 14 86
P2525 1.99 0.19 Epizone 20.68 0.13 57 29 14 10 90
P289 0.86 0.18 Epizone 31.84 0.10 63 19 18 0 100
P747 1.03 0.18 Epizone 33.5 0.04 48 29 23 0 100
P811 1.79 0.18 Epizone 32.66 0.15 – – – 0 100
SS-3 1.53 0.15 Epizone 37.1 0.02 – – – 2 98
SS-2 1.83 0.14 Epizone 35.46 0.02 48 31 21 12 88
P3687 3.59 0.15 Epizone 32.92 0.04 42 33 25 18 82
 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142 139

Fig. 2. A positive correlation exists between illite crystallinity and porosity (A), indicating porosity is reduced with increasing maturity and metamorphism. Note illite
crystallinity values decrease with increasing maturity/metamorphism. Percent proportions of macropores and mesopores are determined by porosimetry with micropores
percentage determined by gas adsorption analysis. Both the proportion of macropores (B) and micropores (C) increase with maturity/metamorphism while the proportion of
mesopore (D) decreases with increasing maturity/metamorphism. Micropore volumes are increasing either due to secondary porosity development in kerogen or because of a
relative increase due to loss of mesopores. As the proportion of mesopores is the only size fraction that has a similar trend to porosity reducing with increasing maturity/
metamorphism, it following that mesopores are making the greatest contribution to porosity of this suite of rocks. The increase in macropores is relative which is due to
relative reduction in mesopores. A phyllite sample is shown as an outlier (cross symbol) and illustrates a sample within the epizone can exhibit high porosity (3.6%) and
potentially still have significant gas content within the matrix. Roman numerals refer to samples in Fig. 3; D-51-F-3iso (I), 11-7-16 (II), P747 (III) and P3687 (IV).

trates that a rock that is defined by illite crystallinity as within the
epizone can still have a relatively high porosity value (3.8%)
compared to the rest of the sample suite. The PSD of this phyllite
sample shows a higher than expected macropore volume
compared to other samples in the epizone (Fig. 3). The porosity
of the granite sample is 1.5% and the PSD indicates that porosity
is composed of macropores only, similar to the metamorphic rocks
within the epizone (Table 3).
Discussion
Studies have shown porosity decreases within sandstones and
shales with increasing depth of burial with the exception of shales
that have not dewatered (i.e., Hunt, 1995). This study has
illustrated that porosity in high maturity (dry gas; Ro > 2.0%) shales
and pelitic metamorphic rocks continues to decrease with increas-
ing maturity-metamorphic grade and porosity values are below 2%
within the epimetamorphic rocks (Fig. 2A). PSD from mercury
porosimetry and gas adsorption analyses indicate that as this suite
of rocks increase in maturity and metamorphic grade, there is an
increase in micropores volumes and macropore volumes and
decrease in mesopore volumes. We postulate the loss of mesopores
is due to the increase in illite crystallinity and recrystallization and
growth (authigenesis) of the illite and muscovite grains during dia-
genesis/metamorphism. The increase in micropore volumes may
be associated with secondary porosity development within the
organic fraction (Jarvie et al., 2007; Chalmers and Bustin, 2008a;
Chalmers et al., 2012a) although these rocks are TOC lean (<1.5%)
as well as a decrease in mesopore volumes may create an illusion
of an increase in micropores. Micropore volume may also increase
due to growth of illite crystals with metamorphism, studies have
shown illite does have micropore volume (i.e., Ross and Bustin,
2009). The increase in macropores with increasing diagenesis and
metamorphism is an unexpected result as studies have shown
macropore volumes reduce with increasing maturity in potential
shale gas reservoirs (i.e., Chalmers and Bustin, 2012a), although
in this example, samples are lower maturity (Ro between 0.77%
and 1.22%) and contain larger volume of macropores compared
to samples in this study. The increase in macropore volumes iden-
tified in porosimetry analysis (Table 3) may be related to the
decline in mesopore volumes with increasing maturity/metamor-
phism. Incremental pore volume data and the positive relationship
between mesopore volume and maturity/metamorphism illustrate
the important contribution mesopores make to the total porosity
(Fig. 3). It follows that by combining the observations from this
study with the observations made in the study by Chalmers and
Bustin (2012a), the destruction of porosity is the result of the loss
of macropores in lower maturity shales (immature, oil to wet gas;
Ro < 2%) whereas the reduction in mesopore size fraction is the
cause of decreasing porosity values in higher maturity shales
(dry gas; Ro > 2%). We postulate the reduction in macropores in
lower maturity shales is related to mechanical processes with the
loss of mesopores in higher maturity shales related to less mechan-
ical and more chemical processes that involve the recrystallization
and growth of illite and muscovite. Due to limited sample size and
volume, thin section analyses could not be performed for this study
to verify illite growth reduce mesopore volumes and future work
should include thin section with back-scattered electron
microscopy.
The relationship between porosity and illite crystallinity
provides a framework for exploration of plays that have undergone
140 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142

Fig. 3. The PSD by incremental pore volume for four samples that range in porosity and illite crystallinity (see Fig. 2A) to illustrate the different contributions made by
mesopores and macropores to the total volume of porosity in this suite of rocks. The difference in the bulk density measured from mercury immersion technique and mercury
porosimetry is less than 3.3% which indicates the porosity in the 10,000–100,000 nm range is not an artifact of intergranular porosity that may be measured between crushed
grains during the porosimetry analysis. The outlier (E) illustrates that a rock that is recognised as a slate in hand specimen and is within the epizone can still contain relatively
high porosity (3.8%) which is comparable to some producing gas shales (i.e., Horn River shales; Chalmers et al., 2012). Roman numerals refer to samples in Fig. 2A; D-51-F-
3iso (I), 11-7-16 (II), P747 (III) and P3687 (IV).

Fig. 4. Relationship between cumulative gas saturation and illite crystallinity (IC). Cumulative gas saturation curve illustrates the proportions of micropores (<2 nm),
mesopores (2–50 nm) and macropores (50–300 nm) for each sample. With decreasing IC values (increasing maturity and metamorphic grade) there is an increase in the
proportion of micropores compared to meso- and macropore volumes.

late diagenesis and low grade metamorphism. Gas in place is
strongly influenced by free gas content as gas-in-place (GIP) esti-
mates (Ross and Bustin, 2008) are calculated by:
GIP ¼ ½sorbed þ free gas capacity
 ½volume of draining reservoir  rock density
Sorbed and free gas capacity is measured in cm3/g, volume of
draining reservoir in cubic metres and the rock density in g/cm3.
The free gas component is proportional to porosity and saturation
(Ross and Bustin, 2007). This proportionality is dependent on the
reservoir pressure, reservoir temperature, water saturation, gas
species and gas compressibility. If these parameters and the sorbed
gas capacity remain constant within a reservoir, then both the free
gas capacity and GIP will decline with a reduction in porosity. To
determine the level of maturity for a porosity cut-off value will
depend on the economic fundamentals of the project (i.e., gas
price, drilling and completion costs, basin geology etc.) and need
to be assessed on a play by play basis. Once a cut off value is deter-
mined, the degree of maturity at which the play is still economical
can be approximated from the relationship in Fig. 2A. For example,
if we assume a porosity cutoff at 3% as in petrophysical models
(Nieto et al., 2009; Glorioso and Rattia, 2012) and producing zones
of the Barnett and Horn River shales (Stevens and Kuuskraa, 2010),
then the reservoir quality is sub-economical at a D2h of 0.38 which
plots within the anchizone (Fig. 2A), although the outlier phyllite
sample (P3687) in Fig. 2A indicates that exceptions exist and
reservoir rocks can be located within the epizone. Although porosi-
ties are lower in deeper unconventional reservoirs, the loss in gas
storage is offset by the increase in reservoir pressure at depth,
 G.R.L. Chalmers, R.M. Bustin / Journal of Unconventional Oil and Gas Resources 12 (2015) 134–142
resulting in an increase in GIP as the gas will concentrate (higher
molarity) due to gas compression; provided the pore pressure does
not exceed the pressure barriers of the rock and cause microfrac-
turing and migration.
The phyllite outlier in Fig. 2A which illustrates porosity of meta-
morphic rocks can be still be relatively high (3.8%) and comparable
to some shale gas plays (i.e., 3–6% for Horn River shales; Stevens
and Kuuskraa, 2010) contradicts the assumption that low grade,
pelitic metamorphic and granitic rocks have little to no matrix
porosity (Biryukov and Kuchuk, 2012). Further investigation is
needed into why this phyllite still contains a relatively high pore
volume. This study further illustrates natural fractures are not
the only source of free gas within metamorphic rocks but a signif-
icant portion of the gas can be located within matrix porosity.
Higher than expected porosity for low grade pelitic metamorphic
rocks, has implication on exploration limits of organic-rich shales
that grade into metargillites and slates. These potential reservoirs
should be examined on a case by case basis. These findings should
be incorporated into shale gas exploration models for deeply-
buried organic-rich shale and pelitic metamorphic gas reservoirs.
A negative implication for exploration is that with a loss of the
mesopore size fraction with increasing maturity/metamorphic
grade will reduce the gas flow within the reservoir as shown with
the Horn River and Doig–Montney reservoirs of British Columbia
(Chalmers et al., 2012b; Chalmers and Bustin, 2012b). Mesopores
are interpreted to be essential in providing pathways between
micropores and macropores and increases the matrix permeability
of gas shale reservoirs (i.e., triple porosity model; Chalmers et al.,
2012b; Chalmers and Bustin, 2012b). Permeability anisotropy
(i.e., greater difference between vertical and horizontal permeabil-
ities) is expected to increase with diagenesis and metamorphic
grade as illite and muscovite grains will grow and align parallel
to minimum stress direction. Due to very low permeability for dee-
ply buried shales, fracture stimulation will be an integral part of
well completions for potential pelitic metamorphic rock reservoirs.
Conclusions
This study has shown that the well documented trend of
decreasing porosity with increasing depth of burial (diagenesis)
continues into the later stages of diagenesis and the early stages
of metamorphism (anchizone and epizone). Further conclusions
drawn from this study are:
(1) Porosity reduces to below 2% in rocks that have experienced
epimetamorphic processes, although exceptions occur. This
variation within the epizone indicates that metasedimentary
and low-grade metamorphic rocks should not be assessed as
uneconomical gas reservoirs by assuming that no porosity
remains.
(2) These rocks should be assessed independently on a case by
case when exploring regions with organic-rich shales prograd-
ing to low grade metamorphic rocks (anchizone to epizone).
(3) From studies on shales with maturities in the oil to wet gas
window, the loss of porosity is due to the reduction of
macropore volumes (Chalmers and Bustin, 2012a) while
the reduction in porosity for shales with higher maturities
(Ro > 2%; dry gas) and low grade metamorphic rocks is due
to the reduction of mesopore volumes.
(4) The difference in changes in PSD from a reduction in macro-
pores to a reduction in mesopore volumes could signify a
change from mechanical destruction of pores dominating
in less mature rocks to more chemical dominated processes
of authigenic recrystallization and growth of the illite and
muscovite in more mature rocks.
141
(5) The loss of mesopores will have a negative impact on the
matrix permeability and natural or induced fractures will
be increasingly important aspect of well completions.
Acknowledgements
We would like to thank Greg Dipple and Stuart Sutherland from
the Department of Earth and Ocean Sciences, UBC for providing
metamorphic and granitic samples. We are also grateful for the
analytical work performed by Kristal Li in our research group at
the UBC. We thank NSERC and Geosciences BC for the financial
support of this project.
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