PETROPHYSICS, VOL. 52, NO.

1 (FEBRUARY 2011); PAGE 32-49; 25 FIGURES; 2 TABLES

Laboratory NMR Measurements on Methane Saturated

Barnett Shale Samples
Richard F. Sigal1 and Elijah Odusina1

ABSTRACT
The NMR signature of methane saturated Barnett total gas stored in these pores within its signal.
shale core plugs measured in a non-gradient magnetic field The NMR water signals in Barnett core plugs have T2
is dramatically different from what would be seen if the relaxation spectra with a mode on the order of 1 ms. This
methane relaxed as a bulk fluid. At laboratory temperatures, observation is consistent with either the water being clay
the methane T2 relaxation spectra have modes on the order bound, or at the least the water is located in very small
of 10 ms. This is consistent with a significant percentage of pores that are at least partly water wet.
the methane being located in nanometer scale hydrophobic This study shows that NMR logging measurements
organic pores, and relaxing by a dipole-dipole interaction should be able to provide quantitative estimates of the
with the hydrogen molecules in the organic material. For free gas storage and information on the percentage of free
pores of this size any gradient field diffusion induced gas stored in organic pores. However, this will require
relaxation would be strongly suppressed, consequently development of new interpretation methodologies, and
the effects of internal gradients should be of second order. application of traditional methodologies, based on the
Methane in these pores would not be displaced by invasion gas signature in conventional reservoirs, will produce
of water-based mud, so an NMR log should register the erroneous results.

INTRODUCTION T1 measurements confirm this. This result is in stark

The effort to characterize the Nuclear Magnetic
Response (NMR) response of gas saturated Barnett shale
reservoir rocks is an ongoing research effort. The work
completed to date has concentrated on T2 measurements.
These show that NMR logging has an important place
in shale gas reservoir characterization, and that applying
the traditional NMR interpretation methods for gas
identification will lead to erroneous conclusions.
The major results of this work are
(1) the primary relaxation mode for methane in Barnett
shale samples is surface relaxation;
(2) the NMR measurement detects all the methane injected
into the sample that is stored as free gas and;
(3) the injected gas completely represents the free gas
storage capacity of the sample.
The surface relaxation mode, at laboratory temperature,
has a gas relaxation with its primary T2 relaxation time
constant at about 10ms. Since this relaxation is primarily
due to surface interaction it also means that the T1
relaxation will be comparably fast. Some very preliminary
contrast to the relaxation of bulk methane, where T1 is
several seconds. The standard NMR interpretation assumes
that relaxation is predominantly through the bulk relaxation
mode. This assumption will lead to the failure to identify
the fast-relaxing signal as methane. The water in Barnett
shale samples relaxes with a primary time constant around
1ms. Because both the methane and water spectra have
a width of more than a decade at laboratory temperatures,
there is significant overlap between the water and gas signal.
The measurements performed for this study have been
refined over the time of the project. The major driver of
the refinement was to improve the quantitative results.
The data discussed in this report will mainly be restricted
to measurements done with the improved methodologies.
Earlier measured data is qualitatively similar to the data
reported here.
BACKGROUND
Traditional methane detection using NMR logging
tools depends on the assumption that there is no surface

Manuscript received by the Editor December 12, 2010; revised manuscript received January 14, 2010.
1
Mewbourne School of Petroleum & Geological Engineering, University of Oklahoma, Norman, Oklahoma, USA, 73019-1003;
Email: rsigal@ou.edu, elijah.o.odusina-1@ou.edu
©2011 Society of Petrophysics and Well Log Analysts. All Rights Reserved.

32 PETROPHYSICS December 2010

 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples
relaxation effect in the methane relaxation spectrum (Coates
et al., 1999). That is the methane relaxation is given by
1 1 1 that these conditions do not apply.
= + and
T2 T2 Bulk T2 diffusion
1 1
= .
T2 Bulk T1Bulk
T2Bulk is the transverse relaxation time component
produced by the interaction of the fluid with itself; T1Bulk
is the longitudinal relaxation time component produced by
the fluid interaction with itself; and T2diffusion is the transverse
relaxation time component produced by de-phasing due to
diffusion of the molecules in a gradient magnetic field. The
diffusion affects transverse but not longitudinal relaxation.
It is a general result that in all cases the transverse relaxation
time is less than or equal to the longitudinal relaxation time.
For the magnetic field strengths used in logging and benchtop
measurements, the bulk relaxation mechanizations for fluids
produce the same bulk relaxation rates. Differences in
observed relaxation are due to either, diffusion when there is
a magnetic gradient, or when surface relaxation mechanisms
dominate the measurement.
T2 , transverse relaxation measurements, in the study
were acquired by a Carr, Purcell, Meiboom, Gill (CPMG)
pulse sequence. This is the same sequence typically used in
wireline logging. For this case
2
1 D (γ G TE )
= ,
T2 diffusion 12
where D is the bulk diffusion coefficient for methane, γ is
the gyro magnetic ratio, and G is the magnetic field gradient,
and TE is the echo spacing (Coates et al., 1999). The pre-
conditions for the previous equations are that the gas must
be non-wetting and exist well away from the pore walls to
avoid surface relaxation effects, and that the pores are large
enough, or well enough connected, that their size does not
limit the distance the methane can diffuse during the time
taken for relaxation. At reservoir conditions for typical
logging tool gradients and pore geometries this requires pore
sizes larger than approximately 50 microns.
In the NMR logging of conventional gas reservoirs
using water-based mud, invasion is deep enough that the
NMR measurement is responding to gas in the invaded
zone. In the invaded zone there will be high water saturation,
and as gas is typically non-wetting the gas is located in
the center of the pores, with a thick water layer shielding
the gas from the pore walls and preventing any surface
relaxation effects. Also, the pores in conventional reservoir
rocks are usually large enough that using the bulk diffusion
coefficient does not seriously compromise the predicted
relaxation time. Consequently, for conventional reservoirs,
February 2011
equations (1)–(3) are good approximations, and can be used
to design gas identification algorithms. Unfortunately, the
current understanding of shale gas reservoir rocks shows
(1) Organic shales of sufficient maturity have generated gas
from their organic materials. Studies combining ion milling
of the shale surfaces, and nanometer resolution SEM, show
that the organic material in the shale contains significant
(2) porosity (Passey et al., 2010; Sondergeld et al., 2010). The
observed intra-organic pores have approximately circular
cross-sections with characteristic diameters on the order of
1 to100 nm. In the ion milled 2-D cross-sections, and 3-D
reconstructions, the organic material appears to occupy
zones of a few microns.
The pores in the organic materials are hypothesized
to have been formed by the gas and oil generated from
the organic material. Under these conditions they did not
originally contain water. Further, this organic material
is very likely hydrophobic meaning that in a gas/water
system, gas preferentially wets the surface. It would also be
expected, that in an oil/gas system, oil would preferentially
wet the surface. (This explains the observation that there is
significant oil based mud invasion in the Barnett.)
The gas in the organic material will be in contact with
the pore walls and there will probably be no water in these
pores. This gas should therefore have a surface relaxation
component that will affect both T1 and T2 relaxation, and
probably cause them to be unequal. Because of the small
dimensions of the pores and the organic zones, the diffusion
relaxation component of the T2 relaxation curve should be
strongly suppressed. Thus the standard assumptions, and
the equations based on them, (that are used to identify the
(3) presence of gas in an NMR log response) do not apply to the
gas in the intra-organic pores (abbreviated to “organic pores”
in the remainder of the manuscript). A further observation is
that as these pores are on the nanometer scale there will be
very strong capillary forces. These forces will keep water
out of these pores so the gas in the organic pores will not be
displaceable by water based mud.
Organic shales are also observed to contain water, most
of which exists as clay bound water. However, it is possible
that there are pores that are water or fractionally wet that
could also contain gas. If that gas is in the invaded zone it
would be partly displaced and the remainder could produce
a bulk gas response. These pores should also be very small
so the diffusion relaxation component on their T2 spectrum
should be suppressed. Because of the very low permeability
of organic shales the depth of the invaded zone should be
shallow enough that NMR logging tools, with variable
depths of investigation, could quantify the number of gas
molecules contained in-situ in all the pores, not just the
organic pores. In fact, by varying depth of investigation it
should be possible to quantify the gas in the organic pores
and the gas in water or fractionally wet pores.
The gas in water-wet pores, outside the invaded zone,
will likely have a surface relaxation contribution. Straley
PETROPHYSICS 33
 Sigal and Odusina
(1997) and Winkler et al. (2006) have both shown that, at
low water saturations, gas in water-wet pores relaxes much
faster than its bulk relaxation rate. This relaxation rate may
have a relaxation component produced by internal magnetic
gradients, but the dominant driver is surface relaxation.
The quantification of gas in the reservoir depends on
the ability to separate the NMR signal into a water and gas
component. The gas signal once obtained is a direct measure
of the number of hydrogen atoms contained per unit volume
in the reservoir. This, combined with the gas composition,
provides the number of gas molecules per unit volume. This
estimate is independent of gas pressure and gas porosity. (In
this manuscript gas porosity refers to the fraction of the total
volume, expressed as a percentage, occupied by gas; water
porosity refers to the volume fraction occupied by water.)
The gas pressure when independently determined along
with the equation of state can be used to provide the free
gas volume.
The suppression of diffusion relaxation and the presence
of surface relaxation components for gas in organic shales
imply that the signature of gas on an NMR log, the knowledge
of which is necessary to separate the gas and water signal, is
not known a priori but must be investigated experimentally.
The following sections describe such a program for Barnett
shale samples.
EXPERIMENTAL SETUP
AND PROCEDURES
NMR
The measurements were made on one-inch diameter
one-inch long horizontal samples. Some of the samples
came from core that had been stored in a core warehouse
for several years at room conditions that varied during the
year. Other samples came from core that had been preserved
to maintain the reservoir water saturation. The preserved
core was wrapped, wax coated, and kept frozen. Following
plugging, these samples were kept in a 100 percent humidity
environment at laboratory room temperatures.
The experiments were performed on a 2 MHz benchtop
system. For the measurements reported here no external
magnetic field gradient coil was not used. The measurements
were made in a commercially purchased pressure vessel.
Hydrostatic confining pressure was maintained at 5000
psi using an NMR neutral fluid FluorinertTM to provide the
confining pressure. During the NMR measurement the fluid
was maintained at 35 °C, which was also the temperature of
the magnet.
At the start of the NMR experiment the methane pore
pressure in the sample was established at about 4000 psi.
There is a very small leak in the plumbing of the pressure
vessel that despite extensive efforts could not be corrected.
It led to approximately a one-psi/hour drop in the pore
pressure. Calculations verify that this small loss of methane
should not affect the NMR measurement.
34 PETROPHYSICS
The methane used in the experiment was research grade.
Despite this, unless a vacuum is pulled on the system to
remove the oxygen present due to initial air in the system,
its bulk relaxation rate is faster than that of pure methane.
In order to maintain original water saturation in the samples
the vacuum system could not used, so any bulk methane
relaxation is slightly faster than that of pure methane.
The one-inch sample is jacketed in a shrink-wrap
sleeve. The sleeve material was tested for its contribution
to the NMR relaxation spectrum. There is small very fast
contribution that is at the limit of the system resolution. It is
at a signal-to-noise level where the signal processing is no
longer robust.
The one-inch sample assembly consists of the one-inch
sample, a two-inch long solid-peak cylindrical end piece
at one end, and at the other end a three-inch long peak
distribution head through which the methane is injected into
the sample. O-rings on the peak above and below the sample
provide the seal for the shrink-wrap sleeve. Because methane
remains in the distribution head, its signal must be subtracted
from the NMR relaxation curve to get the relaxation curve
for the methane in the sample. This correction is referred to
as the head gas correction.
The routine system calibrations for the NMR instrument
are done before each measurement cycle. The signal
produced from the shale sample is too small to be used as a
source for these calibrations, so system calibration cannot be
done during different stages of the measurement cycle.
The NMR signal amplitude was calibrated with a
mass of water occupying a volume roughly the same as the
sample volume. The calibration was preformed on water in
a hollow peak cylinder placed in the sample location. The
sample assembly was placed in the pressure vessel and
a small confining pressure was applied. The temperature
of the confining fluid was 35 °C. The calibration factor
used in analyzing the measurements reported here was
independently measured by each of the authors. The
difference between the measurements was 0.4 percent. The
amplitude calibration factor directly relates to the number of
hydrogen atoms in the sample. This allows direct calculation
of the number of methane molecules after the gas signal has
been isolated.
The heterogeneity of the primary magnetic field has
been measured by moving a 0.5 cm thick cylinder of water
from the bottom to the top of the probe and making a 400
scan CPMG measurement each 0.5 cm. Figure 1 shows the
results of that measurement. In the sweet spot where the
one-inch sample is measured (9 cm to 12 cm on plot) the
magnetic field strength varies by 1.6 percent.
The NMR measurement cycle comprises two stages.
In the first stage the gas free sample is placed in the
pressure vessel, which is in turn placed in the magnet sweet
spot, confining pressure is raised to 5000 psi and sample
temperature raised to 35 °C. A T2 measurement is then made
using the standard CPMG method. For this measurement
the echo spacing is 0.3 ms, which is the minimum interval
February 2011
 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples
provided by the instrument. The time between CPMG
measurements,or wait time, is set to 500 ms; 10,000 stacks
are recorded. Previous studies have shown that the water in
Barnett shale samples has a rapid decay time and that there
is no actual signal after about 100 ms. The previous studies
also established that 10,000 scans is adequate to acquire
meaningful data. This measurement provides the NMR
water relaxation curve.
After the water relaxation curve is acquired the sample
is left in place and saturated with methane. The details of
this process will be described in the next section. The gas
plus water NMR relaxation curve is acquired in the second
T2 measurement. It is performed at 35 °C and approximately
4000 psi pore pressure. For this measurement the echo
spacing is 0.3 ms, the wait time is 15 sec, and 10,000 stacks
are acquired. The long wait time is to assure that all the
methane signal is captured. This measurement takes roughly
three days so there is no practical way to significantly
increase the signal-to-noise ratio using the current system.
The relaxation curve for the gas in the sample is
determined by first subtracting the water relaxation curve
from the water plus gas relaxation curve. The gas relaxation
curve contains the spurious signal from the gas located
in the distribution head. Because the primary magnetic
field has a significant gradient in the head, the signal does
not occur at the bulk methane relaxation time. The head
gas signal is removed by subtracting its relaxation curve
from the gas relaxation curve. The head gas correction
has been determined by making a T2 measurement on a
solid peak sample so that the only gas was located in the
distribution head.
Storage Determination
Between the initial measurements of the NMR water
relaxation curve and the final measurement of the NMR
Fig. 1 The magnetic field variability of the primary
magnetic field. The sweet spot runs from location 9 cm
to 12 cm. The height axis is relative to an arbitrary origin.
February 2011 PETROPHYSICS
water plus gas relaxation curve, gas must be injected into the
sample. The method of determining the amount of methane
injected (stored in the shale sample) has been refined several
times as the effect of gas adsorption became clearer. The
current method provides a reasonable estimate of the total
amount of gas injected, but does not provide an independent
ability to resolve the total into adsorbed and free components.
The method quantifies the amount of gas added by a series
of pressure drop experiments. Figure 2 provides a general
schematic of the apparatus. The pressure vessel shown in the
figure sits inside the NMR system. The NMR system itself,
together with equipment to control temperature and raise the
gas pressure, are not shown. During pressure measurements
the confining fluid is kept at room temperature to minimize
the temperature gradients. This requires active cooling as the
vessel sits inside the NMR magnet, which is heated to 35 °C.
Each pressure drop stage starts with valve 2 closed. To start
V1 , volume 1 is raised to a pressure P1 , and then valve 1 is
closed. Volume 3, the sample and dead volume V2 are at
an initial starting pressure P2 . The test consists of opening
valve 2 and recording the pressure as a function of time until
it has stabilized at a new pressure Pf . For each stage P1 is
greater than P2 . Three stages are usually required to get to a
final pressure of about 4000 psi.
The analysis of a given stage proceeds as follows. Moles
of methane n1 in V1 at pressure P1 are given by
P1 V1
n1 = , (4)
z1 RT
where R is the universal gas constant, T is the temperature
and z1 is the correction factor that accounts for deviation
from the ideal gas law. The correction factor depends on
temperature, pressure and the type of gas. Supertrapp, a
program produced and distributed by the National Institute
Fig. 2 The diagram shows the essential features of the
system to measure the amount of gas injected into the
shale sample.
35
 Sigal and Odusina
of Standards and Technology, is used to calculate the z
factors. Similarly the moles of gas contained in V2 initially
are given by
P2 V2
n2 = . (5)
z2 RT
After valve 2 is opened and the pressure has stabilized at
Pf , n1 f , the moles in V1 , and n2 f , the moles in V2 , are
given by
Pf V1
n1 f = and (6)
z f RT
Pf V2
n2 f = . (7)
z f RT
Mass balance requires that the decrease of moles of gas in
V1 , Δn1 , is equal to the increase in moles of gas in V2 , Δn2 ,
plus the increase in moles of gas stored in the sample, Δns .
From the previous equations
Δ n1 = V1 ( P1 z1 − Pf z f ) RT , (8)
( )
Δ n2 = V2 Pf z f − P2 z2 RT , and (9)
Δ ns = Δ n1 − Δ n2 . (10)
The sum of the Δns over the pressure drop stages
provides the total amount of gas stored in the sample. The
gas is stored as both free and adsorbed gas. These volumes
are linked as the volume of adsorbed gas increases, it
decreases the volume available for free gas, unfortunately
separating these volumes is difficult as there is insufficient
information from these storage measurements to separately
identify the amount of free and adsorbed gas.
The volumes V1 and V2 were established by
measurements similar to those described above using steel
samples with precisely known pore volumes. Based on
multiple measurements using three samples for V1, the ratio
of the standard deviation of the measurements to its average
value is 1.6 percent, and the ratio for V2 is 2.5 percent.
The storage measurements had to be corrected for the
small uncontrollable leak in the pressure vessel. The very
low permeability of the shale samples causes it to take several
hours to reach pressure equilibrium after valve 2 is opened.
36 PETROPHYSICS
Because of the leak the pressure never stabilizes, but does
become linear with time. Each pressure drop experiment is
continued until this linear trend is clear, and then this trend
is used to correct the pressure drop and obtain Pf . During
some periods the lab suffers temperature variations over the
time of the storage measurement that affect the accuracy of
the measurement.
Once the methane pressure in the shale sample has been
raised to about 4000 psi valve 2 is closed to isolate the pressure
vessel and the shale sample inside it. The temperature of the
confining fluid in the pressure vessel is then raised to 35°C
and an NMR measurement is done to obtain the gas plus
water relaxation curve. Raising the temperature results in
about a 5 percent increase in pore pressure.
DATA ANALYSIS AND DISCUSSION
The NMR relaxation curves M(t) were processed to
obtain their NMR spectral representation. The spectral
representation was obtained by modeling M(t) as a sum of
64 decaying exponentials. That is expanding M(t) as
64
M (t ) = ∑ Ai e
− t Ti
(11)
i =1
then inverting for the Ai values. This problem is ill posed so
the inversion has to be regularized. The noise level is used to
set the regularization.
The inversion process for each relaxation curve was
carried out using the software package supplied by the
manufacture of the NMR system. In using their software the
64 decaying exponentials were chosen to have time constants
logarithmically spaced between 0.1 ms and 30 seconds.
The noise estimate used to control the regularization was
determined from the asymptotic signal.
The data discussed in this report were measured on five
preserved samples and five unpreserved samples. Three of
the preserved samples were from Well 1 and two were from
Well 2. The five unpreserved samples were from Well 3. Each
sample is assigned unique sample identification number.
The data in this study is very noisy and the signal decays
very fast. This is especially true for the water relaxation curve.
Figure 3 shows the water relaxation curve for Well 1 sample
6366.58. As this is a preserved sample it should contain most
of the original formation water. Reviewing the results, the
NMR relaxation curve clearly sinks into the noise by 2.5 ms.
A data point is recorded every 0.3 ms so there are basically
eight points defining the spectrum. The issue is both the low
signal-to-noise and the rapid relaxation. If the relaxation had
a larger time constant the signal would be much better defined
even with the same asymptotic noise level. Figure 4 shows
the water relaxation curve from Well 3 sample 7621. As this
sample was not preserved the maximum signal amplitude is
less, but everything else is similar to the preserved sample.
February 2011
 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples

Fig. 3 Water T2 relaxation curve for sample from 6366.58 ft from Well 1. The signal has dropped into the noise by
2.5 ms. (i.e., 25,000 µs)

Fig. 4 Water T2 relaxation curve from sample 7621 Well 3. The signal has dropped into the noise by 2.5 ms.

February 2011 PETROPHYSICS 37

 Sigal and Odusina

The water plus gas relaxation curve from Well 1 sample
6366.58 is shown in Figure 5. There is clearly more signal
and the presence of slower relaxing components. Some of the
slow relaxation is contributed by the head gas signal, which
has not been removed from the relaxation curve. Because
of the rapid relaxation and low signal-to-noise ration the
inversion performed to obtain the water spectrum is not as
robust as is usually the case. The general spectrum shape is
relatively robust but the signal amplitude is an issue.
the signal has been separated into components, each with
approximately the same hydrogen index.
The water signal shown in Figure 6 represents a water
volume that is about 3 percent of the pore volume. This is
consistent with earlier NMR measurements on preserved
samples from a different Barnett well that had NMR
water porosities between 2.9 and 3.9 percent. The primary
relaxation peak has its mode at less than 1 ms. which is
consistent with a large number of other Barnett NMR

Well 1 Sample 6366.58

Figures 6, 7 and 8 show the water spectrum, the gas

spectrum and the water plus gas spectrum for the NMR
T2 measurements on the one-inch horizontal core sample
6366.58 ft from Well 1. The gas spectrum was obtained
by subtracting the relaxation curve shown in Figure 3 from
that shown in Figure 5. Both the gas T2 relaxation curve
and the water plus gas relaxation curve were corrected for
the presence of the head gas. Each figure shows both the
incremental and the cumulative spectra. The gas and water
spectra are normalized to the porosity that the measured
volume of fluid represents, assuming all the gas is free gas.
The joint gas and water spectrum is normalized to one, as
volumes cannot be determined from an NMR measurement Fig. 6 The incremental and cumulative T2 water spectra
that contains fluids with different hydrogen indices until for Well 1 sample 6366.58.

Fig. 5 Water plus gas T2 relaxation curve from Well 1 sample 6366.58.

38 PETROPHYSICS February 2011

 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples

measurements. In conventional reservoir rocks this would determination. Three pressure drop stages were required
be associated with clay bound water. Because all of the to get the sample pore pressure to a pressure of 4004 psi
pores are very small in these rocks, it would not be correct to at room temperature. Using the equations from the storage
conclude that all the water detected is associated with clays. section, the total number of moles of methane stored in the
The water relaxation curve implies the water is in pores sample at the start of the NMR measurement was 0.00901
that have pore walls with a significant surface area that is moles. The amplitude of the NMR relaxation curve for
water wet. gas M( t )gas evaluated at t = 0, M( 0 )gas , represents the total
In almost all of the NMR T2 measurements on samples number of hydrogen atoms in the gas detected by the NMR
containing water that have been performed in this project in the sample. Converting this to moles of methane CH4
there is a secondary peak that occurs at relaxation times gives 0.00748 moles. The difference is 0.00153 moles.
between 10 and 100 ms. Because of the relative lack of A Langmuir isotherm for a sample in Well 1 six feet
robustness in the signal processing it is not clear if this from sample 6366.58 had a Langmuir pressure Pl of 1337 psi
secondary peak represents actual information about the and a maximum storage Samax of 48.6 scf/ton, which converts
pore network. The traditional interpretation of NMR would to 0.000157 moles/cm3 . The measurement was made at 79.4°C.
be that the secondary peak represents larger pores, but
that interpretation depends on the assumption that surface
relaxivity is approximately a constant. In this case the
secondary peak could represent water in pores with a pore
wall that is partly organic material (not water wetting) and
partly inorganic material. The organic material would serve
as a weak relaxing surface for the water and thus could cause
the pores to appear larger.
Figure 7 shows the T2 incremental and cumulative
gas spectra. Its primary peak has its mode about one
decade slower than water primary peak, however there is
considerable overlap. The primary peak suggests 3.9 percent
gas porosity. There is a secondary peak that occurs at a time
appropriate for the bulk relaxation time of methane. This
secondary peak contains about 15 percent of the total gas
detected by the NMR measurement and does not appear to
be an artifact. All of the gas spectra observed have such a
peak. All of the samples are horizontal plugs that contain
visible cracks most likely produced by stress relief as the Fig. 7 The incremental and cumulative T2 gas spectra for
core was raised to the surface. This gas is quite possibly Well 1 sample 6366.58.
located in these cracks. If so, this secondary peak would
not be seen on a subsurface log. A sample discussed later
was measured at two different pore pressures. The change
in the amount of gas in the slow mode is consistent with
storage in a crack. The very sharp boundary to the primary
peak is unusual looking. It is introduced when the head gas
correction is made. It is not clear why this happens.
Figure 8 shows the incremental and cumulative spectra
for the water plus gas T2 relaxation. The relaxation curve
had the head gas correction applied. The combined spectra
have a secondary peak at the bulk relaxation time of methane
that is due to gas in stress relief cracks. There is no evidence
for the secondary peak seen on the water spectra (Figure 6).
This peak is partially suppressed in the incremental spectrum
produced from the relaxation curve that did not have a head
gas correction but there are still non-zero values between 20
and 100 ms. in that spectrum. It is not clear why making the
head gas correction produces the complete suppression seen.
The storage for sample 6366.58 was estimated using Fig. 8 Water plus gas incremental and cumulative T2
the methodology described in the section on storage spectra for Well 1 sample 6366.58.

February 2011 PETROPHYSICS 39


Using the Langmuir equation
S = S amax ( P Pl ) (1 + P Pl ) ,
where P is the pore pressure, 4004 psi. This gives an
estimated 0.00154 moles stored as adsorbed gas in a one-
inch sample. The amount of gas adsorbed decreases with
increasing temperature so all other things being equal, this
is an underestimate of the adsorbed gas. This is very close
to the difference between the total gas stored and the gas
detected by the NMR. In this case the NMR T2 relaxation
appears to be only measuring the free gas in the pore space.
From the method of constructing the NMR T2 gas
relaxation curve from the water relaxation and the gas plus
water relaxation it would be expected that
M (0) − M (0) = M (0) . (13)
water + gas water gas
In this equation M(0) is the number of hydrogen atoms
represented by the amplitude of the NMR signal. Since the
NMR signal is calibrated to grams of water its primary unit
is grams of water. The actual total number of hydrogen
atoms in the signal is the back projection to zero time of the
relaxation curve. M(0) is an estimate of the back projection
to zero by transforming to the spectral domain and summing
the spectral components.
In this case
M (0) − M (0) = .14 and
water + gas water
M (0) = .27 .
gas
Fig. 9 The cumulative and incremental NMR T2 spectra
for water only for Well 1 sample 6366.78.
40
Sigal and Odusina
There is a considerable difference in the left and right side
of the Equation (13). This is mostly due to the noise in the
value of M(0)water . The previous discussion of the noise in
(12) the various relaxation curves, and its effect on the spectral
transformation, supports this. Analysis later in the section
will further support this conclusion.
Well 1 Sample 6366.78
This sample is a companion sample to the previously
discussed case. It would be expected that the measurements
are very similar, as is generally the case. The amplitude of
the water signal as estimated from the spectral components
is the exception. Figures 9, 10, and 11 show the cumulative
and incremental NMR T2 spectra for the water only case, the
gas only case, and the water plus gas case.
The general observations made on the spectra from
sample 6366.58 all apply to the spectra from 6366.78. The
(14)
(15) Fig. 10 Cumulative and incremental NMR T2 spectra for
the gas only for Well 1 sample 6366.78.
Fig. 11 Cumulative and incremental gas plus water NMR
T2 spectra for Well 1 sample 6366.78.
PETROPHYSICS February 2011
 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples

spectral shapes are almost identical. The gas porosity for in the amplitudes for the water spectral samples is due to
both samples is about 4.5 percent. The water porosities errors introduced in the spectral decomposition, not intrinsic
though are somewhat different. Examining the NMR spectral problems with the NMR water relaxation curve.
amplitudes at zero time shows very good agreement for the For sample 6366.78 the starting pore pressure for the gas
water plus gas case and the gas only case. plus water NMR T2 measurement was 3978 psi. That pressure
was achieved through a three-stage pressure buildup. The
M (0) (6366.58) = 0.5071 (16) calculated number of moles stored in the sample as free
water + gas
and adsorbed methane is 0.00927. The calculated storage
for sample 6366.58 was 0.00901 moles so the difference is
M (0) (6366.78) = 0.4969 (17) 2.89 percent.
water + gas
The NMR gas measurement detected 0.00736 moles
The percentage difference is 2.05 percent. of methane. The estimate of adsorbed methane from the
Langmuir measurement on the sample from six feet away
M (0) (6366.58) = 0.269 (18) was 0.00154 moles. The difference between the methane
gas
storage in 6366.78 and the NMR gas detected is 0.0019
moles. This is similar to the adsorbed gas storage although
M (0) (6366.78) = 0.265 (19) the difference is somewhat more than for sample 6366.58.
gas

The percentage difference is 1.51 percent. Well 1 Sample 6454.95

On the other hand
Figures 12, 13, and 14 show the cumulative and incremental
M (0) (6366.58) = 0.3675 and (20)
NMR T2 spectra for the water only case, the gas only case,
water and the water plus gas case for Well 1 sample 6454.95.

M (0) (6366.78) = 0.4969 . (21)

water

The percentage difference is 35.2 percent.

This comparison shows that the gas plus water NMR
T2 spectra and the gas NMR T2 spectra are quite robust. For
companion samples the spectral signatures are very similar,
and the number of hydrogen atoms detected differs by only
2 percent. The gas plus water amplitudes can be interpreted
as representing what the sample porosity would be if all
the hydrogen atoms were located in water molecules. The
two sample porosities would then be 3.94 percent and
3.86 percent, which is well within the acceptable standards
for a porosity measurement.
The gas only response was constructed from subtracting
the water relaxation curve from the gas plus water relaxation
curve. The similarity of the spectral amplitudes of the gas Fig. 13 Cumulative and Incremental T2 gas spectra for
plus water spectra for the companion samples and the gas Well 1 sample 6454.95.
only spectral amplitudes implies that the lack of equality

Fig. 12 Cumulative and incremental NMR T2 water Fig. 14 Cumulative and Incremental T2 gas plus water
spectra for Well 1 sample 6454.95. spectra for Well 1 sample 6454.95.

February 2011 PETROPHYSICS 41

 Sigal and Odusina

The spectra for Well 1 sample 6454.95 are qualitatively very
similar to the spectra for the previous samples. The water
porosity is at the low end of that measured for preserved
state samples, the water secondary peak is sharper, and the
water relaxation slightly slower. The gas porosity is slightly
higher than for the previous samples.
At the start of the NMR measurement the methane pore
pressure at room temperature was 3980 psi. The methane
was added by the same three-stage procedure as for the
previously discussed samples. The total gas injected was
0.0101 moles. The NMR signal showed 0.00831 moles for
a difference of 0.0017 moles. The Langmuir isotherm at
79.4 °C for a sample from 17 ft away had Pl = 1740 psi
and Samax of 69.5 scf/ton so that the calculated adsorbed gas
storage at 3980 psi for the sample is 0.00204 moles. This
is 20 percent larger than the difference between the gas
signal amplitude from the NMR and the measured amount
of gas stored.
For this case the spectral amplitudes all agree. That is
than for the previous samples. The fast-relaxing gas mode
has its peak value at 4.5 ms, which is faster than for the
previous samples. The gas porosity is also higher than for
other samples. From the measured Langmuir isotherms this
sample has significantly more adsorbed gas. This probably
correlates with the higher NMR gas volume. The gas plus
water spectrum is similar to those observed in the Well 1
samples.
At the start of the NMR measurement the methane pore
pressure at room temperature was 3923 psi. The methane
was added by the same three-stage procedure as for the
previously discussed samples. The total gas injected was
0.0109 moles. The NMR signal showed 0.0104 moles for
a difference of 0.0005 moles. The Langmuir isotherm at
82.2 °C for a sample from eight ft above had Pl = 1323 psi
and Samax of 142.3 scf/ton so that the calculated adsorbed gas
storage at 3923 psi for the sample is 0.00445 moles, which
is an order of magnitude larger than the observed difference
between the total moles of stored methane and the NMR gas

M (0) (6454.95) − M (0) (6454.95) = M (0) (6454.95) .

water + gas water gas
(22)
(0)
water
(6454.95) = M (0) (6454.95)
gas
.

The top half of Equation (22) has a value of 0.2904 and the
right side a value of 0.2991. The percentage difference is
3 percent.

Well 2 Sample 7529.6

Figures 15, 16, and 17 show the cumulative and

incremental NMR T2 spectra for the water only case, the gas
only case, and the water plus gas case for Well 2 sample
7529.6.
The gas and water spectra are again similar to what
was seen in the Well 1 samples. Both the fast and the
Fig. 16 Cumulative and incremental NMR T2 gas spectra
for Well 2 sample 7529.6.
slow-relaxing modes for the gas distribution are narrower

Fig. 15 Cumulative and incremental NMR T2 water Fig. 17 Cumulative and Incremental T2 gas plus water
spectra for Well 2 sample 7529.6 spectra for Well 2 sample 7529.6.

42 PETROPHYSICS February 2011

 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples

signal. In this case the amount of gas measured by the NMR The Langmuir isotherm for a Well 2 sample eight feet
measurement is about equal to the total gas injected into the below at 82.2 °C had a Langmuir pressure of 1765.36 psi, and
sample. a maximum storage of 141.77 scf/ton. Using the Langmuir
Examining the spectra amplitudes at zero time equation the estimated number of moles of adsorbed gas is
0.00369 moles. The difference between the total storage and
the gas detected by the NMR measurement is 0.00287, which
M (0) (7529.6) = 0.4589 grams , (23) is 78 percent of the estimated amount of adsorbed gas.
water + gas
The analysis of the NMR decay curves projected back to
zero time again shows a lack of equality.
M (0) (7529.6) = 0.3309 grams , (24)
water
M (0) (7433) = 0.6143 grams (27)
water + gas
M (0) (7529.6) = 0.3756 grams , and (25)
gas
M (0) (7433) = 0.3708 grams (28)
water

M (0) (7529.6) − M (0) (7529.6) = 0.1282 grams M. (0) (7433) = 0.307 grams
water + gas water (29)
(26) gas
(7529.6) − M (0) (7529.6) = 0.1282 grams .
M (0) (7433) − M (0) (7529.6) = 0.237 gram
as water
ms
water + gas water
So that again the water amplitude seems to be in error. (30)
M (0) (7433) − M (0) (7529.6) = 0.237 gram
ms
water + gas water
Well 2 Sample 7433

Figures 18, 19, and 20 show the cumulative and

incremental NMR T2 spectra for the water only case, the gas
only case, and the water plus gas case for Well 2 sample 7433.
In general the three spectra above closely resemble
the spectra of the other preserved state samples. The water
spectrum does not have the ubiquitous secondary mode with
relaxation between 10 and 100 ms. The gas porosity 5.45
percent is on the high end and this may be correlated to
the larger amount of adsorbed gas measured for the Well 2
samples. The water porosity is 2.92 percent, which is typical
for a preserved sample.
The methane injected into this sample was through the
three stage process. The ending pore pressure was 3854 psi
at a temperature of 297.8 °C. Well 2 sample 7433 stored
0.0114 moles of methane during the three stage process. The
Fig. 19 Cumulative and incremental NMR T2 gas spectra
NMR gas signal detected 0.00853 moles. for Well 2 sample 7433.

Fig. 18 Cumulative and incremental NMR T2 water Fig. 20 Cumulative and incremental NMR T2 gas and
spectra for Well 2 7433. water spectra for Well 2 sample 7433.

February 2011 PETROPHYSICS 43

 Sigal and Odusina

For Well 2 sample 7433 an NMR measurement was also
done at 3027 psi. The purpose of this measurement was to
investigate the nature of the gas signal that shows up at the
bulk methane relaxation time. The most likely explanation
of this signal is that it is methane in the stress relief cracks
visible in the samples. At constant confining pressure the
aperture of a crack is much more sensitive to the value of
pore pressure than is a typical pore body. The images of the
pores in the organics have circular cross sections and thus
are much less compressible than cracks or slit-like pores.
Therefore if the slow-relaxing component is due to gas in
a crack the ratio of the volume of gas in the slow-relaxing
mode to the volume of gas in the fast-relaxing mode should
increase as pore pressure increases. Figure 21 shows the
NMR T2 gas spectra for 3027 psi.
For 3027 psi pore pressure the methane porosity in the
fast-decaying mode is 5.21% and the porosity in the slow
mode is 0.25%. For 3854 psi pore pressure the fast-decaying
mode had 4.95 % porosity and the slow mode had 0.50%
porosity. This gives for 3854 psi the ratio of the volumes in
the two modes is 10.1% while for 3027 psi the ratio is 4.7%.
This large increase in the ratio as pore pressure increases
is most easily explained by the slow decaying gas being
located in cracks. The NMR gas volumes for the fast modes
are very similar, which is consistent with the assumption that
the fast-decaying mode occupies pores that are not slit-like.
Because the samples were not preserved the water signal
is in general somewhat less than for the preserved samples.
This makes the water porosity even less robust, and the
water spectral shape more variable. The NMR gas porosity
though is a robust measurement. Figure 22 provides a plot
of the NMR T2 incremental gas only porosity spectra for the
five samples and Figure 23 for the NMR T2 cumulative gas
porosity spectra.
The Well 3 gas spectra are similar to the gas spectra
for the preserved samples. They all have a small bulk
gas response due to methane in stress relief cracks. The
modes of the fast-relaxing part of the spectra range from
5.4-to-12.3 ms. This compares to 4.5-to-8.2 ms for the
preserved state samples. The Well 3 total NMR T2 gas
porosities range from 3.2 percent to 5.2 percent, while
the preserved state samples range from 4.6 percent-to-
6.6 percent.

Well 3 Samples

The five Well 3 samples (7259, 7508, 7591, 7621,

and 7694) were all unpreserved samples, and by the time
of these measurements had been stored in a core warehouse
for several years. For these five samples the amount of gas
injected into the samples was not precisely measured. A two
stage measurement process was used which provided the
moles of methane stored at about 3500 psi pore pressure and Fig. 22 NMR T2 incremental gas porosity spectra for the
then the pressure was raised to 4000 psi without measuring five Well 3 samples.
the amount of additional gas injected.

Fig. 21 NMR T2 incremental and cumulative gas only Fig. 23 NMR T2 cumulative gas porosity spectra for the
spectra for Well 1 sample 7433 at 3027 psi pore pressure. five Well 3 samples.

44 PETROPHYSICS February 2011

 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples

TABLE 1: Comparison of total amount of gas stored in sample to the estimate of adsorbed gas and the amount of gas detected by
the NMR measurement.
NMR Gas Adsorbed Gas Total Storage
Sample # Δn = nT − nNMR 100 ( Δn − nA ) / nA %
nNMR (moles) nA (moles) nT (moles)
Well 1 6366.58 .00748 .00154 .00901 .00153 −0.65
Well 1 6366.78 .00736 .00154 .00927 .00191 24.0
Well 1 6454.95 .00831 .00204 .0101 .00179 −12.3
Well 2 7529.6 .0104 .00445 .0109 .0005 −88.8
Well 2 7433 .00853 .00369 .0114 .00287 −22.2

Figures 24a and 24b are plots of the Well 3 NMR T2
incremental water porosity. Sample 7508 had an anomalously
high water porosity so Figure 24b shows the incremental
curves with this sample removed. Because the unpreserved
samples have less water than the preserved samples the
spectra are more variable. They all show a small slower
relaxation mode between 10 and 100 ms. Samples 7591 and
7621 have a bimodal fast-relaxation component. However,
the very low water content and the very noisy signal mean
that details of the spectra probably are not significant.
Figure 25 shows the Well 3 samples cumulative NMR T2
water porosity spectra. With the exception of the anomalous
water porosity for sample 7508 the unpreserved samples
show about half the amount of water as the preserved
samples. Although the water amplitudes are not robust at
least the expected trend is still visible.

DATA SUMMARIES AND GENERAL DISCUSSION

From the sample data discussion it has not been clear-cut

if adsorbed gas is a component of the NMR gas relaxation
signal. Table 1 presents a summary of the pertinent sample
measurements.
The actual uncertainties in the measurements in Table 1
are unclear. In the calibration of the storage measurement
the uncertainty in measurement of known volumes is about
0.1 cubic centimeter, which for the methane at 4000 psi
and room temperatures corresponds to an uncertainty of
approximately 0.001 moles. On the other hand for the
companion samples the storage measurement agrees to

Fig. 24a and 24b The top figure displays the Well 3
incremental NMR T2 water porosity for all five samples
and the bottom figure is the same plot with sample 7508 Fig. 25 NMR T2 cumulative water porosity spectra for the
removed. five Well 3 samples.

February 2011 PETROPHYSICS 45

 Sigal and Odusina

TABLE 2: Summary of sample porosity measurements

NMR Gas NMR Water
Sample # Helium porosity % Water Saturation % State
Porosity % Porosity %
Well 1 6366.78 4.06 3.52 7.16 46.4 P
Well 1 6366.58 4.10 2.86 6.26 41.1 P
Well 1 6454.95 4.50 1.74 6.61 27.9 P
Well 2 7529.6 5.98 2.57 6.24 26.9 P
Well 2 7433 4.95 2.92 8.45 37.1 P
Well 3 7259 3.47 1.02 7 - U
Well 3 7508 3.92 3.18 8 - U
Well 3 7591 4.72 1.67 9 - U
Well 3 7621 3.61 1.56 7 - U
Well 3 7694 2.7 1.56 6 - U

0.00026 moles, and the NMR gas measurement agrees to
0.00012 moles. A further source of uncertainty is that the
adsorbed gas measurement is made on a sample that is
displaced several feet from the location of the NMR plug, at
a higher temperature, and on a gound-up sample rather than a
whole plug. It is known that increasing temperature decreases
adsorption, but the other effects are not well quantified.
It is clear though that even if the most optimistic
uncertainty estimate is used, the data on all the samples
except the Well 2 sample 7529.6 is consistent with there being
no adsorbed gas contribution to the NMR relaxation curve.
Sample 7529.6 though presents a problem. The lowest
amount of adsorbed gas storage reported for Well 2 is a
sample 34 ft from this sample. It would give only 0.0024
moles of adsorbed gas, so the estimated adsorbed gas may
be too high. Combining this with the high end of uncertainty
in the storage measurement, and assuming a reasonable
overestimate in the NMR gas measurement, can roughly
reconcile the Well 2 sample 7529.6 measurements. Therefore
at this time it is most reasonable to conclude that adsorbed
gas does not contribute significantly to the NMR signal, but
there is a need for further data.
Table 2 provides a summary of the various porosity
measurements. In Table 2 the NMR gas (methane) porosity
is the total NMR gas porosity minus the gas porosity
associated with the stress relief cracks. This is the porosity
that most likely represents the subsurface gas porosity.
The water porosity is that calculated from the spectral
decomposition. Previous analysis has shown that it has a
more error associated with it than does the gas porosity. The
preserved samples are designated by a P in column 6 and the
unpreserved samples by a U.
For the preserved samples the sum of the NMR gas
and water porosity is consistent with the Helium porosity.
There is certainly no evidence that the sum underestimates
the porosity. In fact the sum seems to be slightly larger than
the Helium porosity. The Helium porosity was obtained by a
low pressure pycnometer measurement on crushed samples
that were dried in a vacuum oven at 100 °C so at least some
of the clay bound water was removed but due to the very
low permeability of the samples some water may have been
left in the sample. The Helium porosity was measured on
end pieces.
In general the preserved samples have a somewhat higher
volume of water than do the unpreserved samples. This is
expected as the unpreserved samples have been drying in
a core warehouse for several years. For these samples the
sum of the NMR gas porosity and the NMR water porosity
is somewhat less than the Helium porosity. For these
samples the Helium porosity was measured on companion
samples rather than end pieces, and so is recorded only to
one significant figure. It is noteworthy that the methane
porosities of the unpreserved samples are generally lower
than the methane porosities of the preserved samples even
though the Helium porosities tend to be higher.
The comparison of the porosities of the preserved
samples with the unpreserved samples and the observation
that the sum of the NMR porosities of the preserved samples
tends to over-estimate the Helium porosity while the sum
underestimates the unpreserved samples’ Helium porosity
strongly implies that the methane and water pore systems are
weakly coupled and methane does not replace water when
the water is removed by a gradual drying process done at
room humidity. In fact it is not clear that a total porosity
measurement is a useful characterization of the samples for
the purpose of resource evaluation.
The spectra of the gas and water responses provide
some information on the wettability of the pore walls. The
very rapid relaxation of the water can only be explained by
a significant fraction of the surface area of the pore walls
of the water containing pores being water wet. It is more
difficult to draw firm conclusions from the methane spectra.

46 PETROPHYSICS February 2011

 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples
The methane that relaxes as a bulk fluid appears to be
located in the visible stress relief cracks. This suggests that
the walls of these cracks are mainly water wet so contain
little organic material. The rapid relaxation of most of the
methane is consistent with it being located in organic pores
that are hydrophobic. The results though of Straley (1997)
and Winkler et al. (2006) show that some of the gas could be
located in pores with pore walls that are water wet as long as
the surface water layer is not too thick. Both the relaxation
spectra and the saturation observations discussed above are
explained by the assumption that the gas is located in the
organic pores and the water in the clay and other inorganic
pores. This is a sufficient, but not a necessary, condition to
explain the observations.
Our measurements were made at laboratory temperatures
not reservoir. For the study of sandstone reservoirs this is
generally not an issue. The water relaxation is known to be
basically independent of temperature (Latour et al., 1992)
and the affect of temperature on bulk fluid relaxation is
well known (Coates et. al, 1999). The evidence though
both from this study and SEM studies on ion milled organic
shale samples (Passey et al., 2010; Sondergeld et al., 2010)
is that a significant amount of methane is located in pores
in the organic materials. The surface relaxation mechanism
associated with the organic pores probably is not dominated
by paramagnetic relaxation. The temperature independence
of surface relaxation on sandstone pore wall surfaces is
explained by the dominance of paramagnetic relaxation.
The Barnett Shale samples generally comprise a few
weight-percent pyrite. (Kale, 2010). SEM images show
some of this pyrite to be located in the organic material.
These are large crystals relative to the observed pore size
of the organic pores and not components of the pore walls.
Consequently, this pyrite is probably not the source of the
methane relaxation.
The dominant mechanism for the relaxation of the free
methane in the organic pores is most likely dipole-dipole
interaction with much less mobile hydrogen nuclei in the solid
organic material and/or the adsorbed methane. Kleinberg in
an unpublished manuscript (2002) discusses dipole-dipole
relaxation. It is temperature dependent with the strength
decreasing with increasing temperature. Kleinberg also notes
that some results in Fung et al. (1981) can be understood as
the, “the abundant, partially immobilized protons in silicon
were very effective in relaxing pore water”.
If the dipole-dipole interaction with the organic material
is the source for the methane relaxation it would be expected
to be weaker at reservoir conditions, so that the methane
response would be slower and thus more easily separable
from the water signal. Also, if the methane spectral signature
is a combination of the relaxation of methane in organic
pores and in low water-saturation inorganic pores, this signal
could also be separated at elevated temperature.
Equation (3) provides the expression for the T2 relaxation
component contributed by diffusion of the gas molecule in
a gradient magnetic field. The magnetic field gradient in
February 2011 PETROPHYSICS
general is a combination of the magnetic field gradient that
polarizes the hydrogen nuclei and magnetic field gradients
produced by susceptibility contrasts in the sample. For these
experiments the polarizing magnet had a zero gradient.
In contrast, standard NMR logging instruments do have a
gradient in their polarizing magnetic fields.
For standard reservoir rocks the diffusion coefficient
can be taken as its bulk value. In this case the logging
tool magnetic field gradient produces, for gas, a diffusion
relaxation rate, 1/T2 diffusion , of roughly 0.02/ms (Coates et al.).
The observed 1/T2 gas relaxation rate in the measurements
reported here is on the order of .1/ms so the logging tool
gradient will have at the most a 20 percent effect on the
relaxation rate. That will move the gas signal with a mode
of 10 ms to a mode of 8.3 ms and narrow the spectral width.
As has been discussed earlier the diffusion coefficient in
equation 3 will be considerably reduced as the pore size and
the organic material deposition reduces total motion to at
most a few microns. The proceeding implies that the logging
tool gradient will not have a significant effect on the gross
features of the relaxation spectrum.
The NMR T2 relaxation spectrum may be influenced
by magnetic field gradients internal to the sample. Because
of the suppression of movement produced by diffusion, the
internal gradients would have to be much larger than that
typically observed in sandstones to produce a diffusion
relaxation rate on the order of the gas relaxation rate
observed. Unfortunately, there is no simple way to estimate
the strength of the magnetic gradients. Simple geometries
such as slit pores or spheres produce a zero gradient so the
gradient field strength is tied up in the details of the pore
geometry. The T2 measurements that have been done do
not provide the data to estimate the internal magnetic field
gradient effect.
Magnetic field gradients do not affect the T1 relaxation
spectrum. An upper bound on their effect would be provided
by the differences between the T1 and the T2 relaxation
spectra. If the gradient field effect is large it would provide a
mechanism to use a combination of T1 and T2 measurements
to separate the gas and water signal. Preliminary T1
measurements on a sample from Well 1 show T1 relaxation
spectra that are qualitatively similar to the T2 measurements,
which implies surface relaxation is the primary relaxation
mechanism, and internal gradient diffusion is at most a
second order effect.
DIRECTIONS FOR FUTURE WORK
There are still significant issues that need to be
investigated to completely clarify the nature of the NMR
response of gas in organic shale reservoir rocks, and to
design a logging program and perhaps new logging tools to
exploit this understanding.
The most obvious direction for future work is to extend
this study to other organic shales. The water and gas spectral
47
 Sigal and Odusina
signatures of the Barnett shales studied are generally fairly
similar. It is necessary to observe how these signatures
change as the nature of the shales change. The percentage
of gas pore space found in the organic material may be an
important variable.
The question of the contribution of adsorbed methane to
the NMR T2 relaxation is not completely resolved. This is in
part a need for more measurements but also a need for more
accurate measurements. The NMR measurement is performed
using 10,000 stacks so improving its signal-to-noise by
additional stacking is not practical. The effect of temperature
on methane NMR T2 relaxation needs to be studied. This is
important both for interpreting logging instrument responses
and for clarifying the nature of the NMR signal.
The current work has mostly measured the T2 relaxation
curve. In general for surface relaxation the T1 relaxation
spectrum is different from the T2 , so it would be valuable to
perform this measurement on all samples. This would both
provide information useful to designing a method to separate
the gas and water signal in a logging environment, and help
to clarify the role of relaxation due to internal magnetic field
gradients in the T2 relaxation curve.
For gas in large pores responding by bulk relaxation,
diffusion has a very strong effect on the measured T2
spectrum. This diffusion affects the T2 spectrum by its own
influence on internal magnetic field gradients produced by
the porous rock, and the large gradient in the logging tool’s
primary magnetic field. The T2 measurements so far have
been completed without an external magnetic field. It has
been argued that the rapid gas relaxation observed combined
with the nanometer scale pore size indicates that diffusion is
much less important in the shale gas case.
It would still be valuable to quantify the effective
diffusivity constant as this will confirm the previous
arguments, and help in designing algorithms to separate the
gas and water signal. It will also provide valuable insight
into the nature of the organic material pore geometry. Some
of the most powerful methods use diffusion to separate gas
and water signals . The current methods used with logging
tools generally do this by making CPMG measurements with
variable echo spacing. Because of the very fast relaxations
involved in the shale case this approach is difficult to
implement. Knowing the effective diffusivity is necessary to
decide if these approaches can be made viable.
All of the work in this study has been with pure methane.
There should be only minor differences to the relaxation if
small amounts of higher molecular weight hydrocarbons are
added. Non-hydrocarbon components will not register on
the NMR signal directly but will change the pressure for the
same number of methane moles and change the diffusivity.
Some measurements with realistic gas components should
be done to quantify these statements.
In some organic shale reservoirs oil or condensates are
being produced. NMR studies with these reservoir fluids
would be very interesting.
48 PETROPHYSICS
CONCLUSIONS
The measurement in the laboratory of the NMR
relaxation spectra of methane saturated samples provided
considerable insight into the nature of the gas storage system
and should be a major component of any shale gas reservoir
study. Preserved samples provide more information than
unpreserved samples but either can be profitably used.
The Barnett shale samples that have been studied contain
water possessing characteristic T2 relaxation time of one ms.
The main part of the water relaxation spectrum has a width
of one to two decades. This rapid relaxation is consistent
with most-to-all of the water being contained in water-wet
clays. It also requires at the least that a significant portion
of the pore wall surface, for pores containing water, to be
water wet.
Unlike conventional reservoirs, the methane also has a
rapid relaxation spectrum. At room temperature the main
part of the curve has a characteristic relaxation of roughly
10 ms and a spectral width of roughly 1.5 decades. It
appears that the adsorbed gas is mainly not included in the
NMR signal.
This rapid relaxation of the gas is for a measurement
without an external magnetic field gradient, so a significant
contribution from surface relaxation mechanisms is
required. For methane contained in organic pores the
surface relaxation mechanism is most likely a dipole-dipole
interaction with hydrogen nuclei in the organic material
and/or the adsorbed gas. This mechanism is expected to
be temperature dependent. The strong surface relaxation
component, combined with the very small pores, implies
that even in the presence of a strong external field gradient
the relaxation from diffusion effects is unlikely to dominate
the methane T2 relaxation spectrum.
Standard gas identification methods depend on the gas
having a large diffusion coefficient and/or a T1 relaxation
decay on the order of seconds. Based on the observations
reported in this paper neither of these is correct for methane
in organic shales. Therefore, applying these algorithms to
NMR measurements in organic shales will result in grossly
incorrect conclusions.
For the Barnett shale a significant amount of gas is
found in organic pores. These pores are hydrophobic so the
gas should not be displaced by water-based mud, and as
such any NMR logging instruments should detect this gas.
Because of the very low permeability of the shale it should
be possible for an NMR tool to have a zone of investigation
outside of the zone invaded by water-based mud filtrate so
all the gas should then be included in the deeper NMR signal.
A variable depth of investigation tool should be able to
distinguish gas in the organic pores from gas in the inorganic
pores. It is further reasonable to expect that an acceptable
correlation can be built to relate the NMR gas signal to the
amount of adsorbed gas. Identifying the quantity of gas in
the organic pores should aid in this. This correlation will
probably be reservoir dependent.
February 2011
 Laboratory NMR Measurements on Methane Saturated Barnett Shale Samples
Based on the above, the NMR logging tool has the
potential at the most to be a stand-alone measurement that
will provide both the total number of molecules of gas present
per unit reservoir volume, and to provide considerable
insight on the nature of the gas storage mechanisms. At the
least it should become an essential component of the shale
gas logging suite.
There are two impediments to this. The first is the size
of the signal from the gas. When hydrogen index effects
are taken into account it will usually represent a one to two
porosity unit signal so slow logging or station measurements
will be necessary. The second is that the rapid gas relaxation
and the relative weakness of diffusion make the separation
of the water and gas signal challenging. Further studies will
be necessary to develop the best way to do the separation.
ACKNOWLEDGEMENTS
Most of the work reported here was supported by very
generous grants from Devon Energy Corporation as part
of a large multi-component study of the Barnett Shale.
Discussions with Ray Ambrose, and Jerry Youngblood both
with Devon have proved very helpful in understanding issues
involved in organic gas reservoirs. Luis Hernandez during
2007-2009 worked on keeping the apparatus functioning
and making measurements. Gary Stowe and Bruce Spears
provided valuable support in keeping the measurement
systems functioning.
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ABOUT THE AUTHORS
In the fall of 2004 Richard Sigal joined the University
of Oklahoma as Unocal Centennial Professor with a joint
appointment in Petroleum Engineering and Geology and
Geophysics. His primary research activity since then has been
on shale gas and other unconventional gas reservoirs. Previous
to this starting in 2001 he worked for Anadarko as part of an
engineering technology group. Most of his work in this group
was concerned with tight gas sands and gas hydrates. Before
joining Anadarko he spent 21 years with Amoco. mostly in their
Tulsa Research Center, and after retiring from Amoco worked
for two years at Halliburton in Houston. During the last 15 years
much of his time was spent on understanding permeability
and the technologies used to characterize and estimate it. He
worked in petrophysics and core measurements at Amoco and
supervised the development of petrophysical applications at
Halliburton. Among his areas of special expertise are NMR, Hg
capillary pressure measurements, and the stress dependence of
permeability.
Richard was trained in mathematics and physics. His
Ph.D. thesis was in general relativity. Since then he has
metamorphosed several times. His first metamorphosis, made at
the University of Alberta, was into the area of surface electrical
measurements. This led to employment in the oil industry with
Amoco, where he was their expert on Magnetotelluric methods.
While at Amoco he gradually became involved with reservoir
characterization, core measurements and petrophysics. Part of
this process was taking and teaching in Amoco’s one-year long
petrophysics training program.
Elijah Odusina graduated with a BS in chemical
engineering from the University of Oklahoma. He is currently
working on his MS degree in petroleum engineering at the same
university. His thesis is focused on NMR properties of shale
rock samples.
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