Journal of Magnetic Resonance 233 (2013) 17–28

Contents lists available at SciVerse ScienceDirect

Journal of Magnetic Resonance

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

Updated methodology for nuclear magnetic resonance characterization

of shales
Kathryn E. Washburn a,⇑, Justin E. Birdwell b
a
Weatherford Laboratories, Houston, TX, USA
b
U.S. Geological Survey, Central Energy Resources Science Center, Denver, CO, USA

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

Article history: Unconventional petroleum resources, particularly in shales, are expected to play an increasingly impor-
Received 6 February 2013 tant role in the world’s energy portfolio in the coming years. Nuclear magnetic resonance (NMR), partic-
Revised 19 April 2013 ularly at low-field, provides important information in the evaluation of shale resources. Most of the low-
Available online 4 May 2013
field NMR analyses performed on shale samples rely heavily on standard T1 and T2 measurements. We
present a new approach using solid echoes in the measurement of T1 and T1–T2 correlations that
Keywords: addresses some of the challenges encountered when making NMR measurements on shale samples com-
Shale
pared to conventional reservoir rocks. Combining these techniques with standard T1 and T2 measure-
Artificial maturation
Solid echo
ments provides a more complete assessment of the hydrogen-bearing constituents (e.g., bitumen,
Dipolar coupling kerogen, clay-bound water) in shale samples. These methods are applied to immature and pyrolyzed
oil shale samples to examine the solid and highly viscous organic phases present during the petroleum
generation process. The solid echo measurements produce additional signal in the oil shale samples com-
pared to the standard methodologies, indicating the presence of components undergoing homonuclear
dipolar coupling. The results presented here include the first low-field NMR measurements performed
on kerogen as well as detailed NMR analysis of highly viscous thermally generated bitumen present in
pyrolyzed oil shale.
Ó 2013 Elsevier Inc. All rights reserved.

1. Introduction
Until recently, the majority of petroleum production has come
from what are often described as conventional resource reservoirs.
These petroleum systems contain three main components: source
rock, reservoir rock, and trap [1]. The source rock contains organic
material called kerogen, which is converted to bitumen and then
oil and gas when subjected to the heat and pressure of burial dur-
ing catagenesis. The produced petroleum may be expelled from the
source rock and then migrate due to buoyancy forces. A trap is a
combination of a low permeability rock in a configuration that al-
lows oil to accumulate. If expelled hydrocarbons accumulate in
rocks with sufficient permeability and porosity, the formation is
said to be reservoir quality.
The decline in new discoveries of conventional reservoirs cou-
pled with improved technologies for exploiting other types of for-
mations has led to increased interest in resources described as
‘‘unconventional’’. While there is disagreement as to the exact
definition of an unconventional reservoir, they are typically de-
fined as reservoirs that do not meet one or more of the traditional
reservoir requirements. For example, the resource may be self-
⇑ Corresponding author.
E-mail address: kate.washburn@weatherfordlabs.com (K.E. Washburn).
sourcing (i.e., the petroleum product has not migrated from an-
other location) or the reservoir rocks may have very low porosity
or permeability.
Oil and gas present in unconventional shale systems account for
a significant portion of the world’s petroleum resources. However,
tHHhe properties and behavior of these systems are still poorly
understood. The challenge of characterizing shales is amplified
by the low permeability of the samples; the permeability of shale
is so low that traditional core analysis methods sometimes fail be-
cause movement of even gases into the rock is difficult to achieve
[2]. This makes the non-invasive nature of NMR an appealing
method for investigating shales.
Shales are relatively unexplored via NMR compared to sand-
stones and carbonates. The reason for this is twofold. First, shales
were not viewed as viable for production and, as such, commanded
less attention. Second, until very recently, low-field NMR equip-
ment, which the majority of NMR measurements made upon por-
ous materials use, had neither the sensitivity to obtain results in a
reasonable period of time nor the technical capability to measure
very short relaxation times, which represent a significant propor-
tion of the hydrogen present in the samples. While some work
with cryoporometry has been performed on shales, the majority
of the measurements have been standard longitudinal (T1) and
transverse (T2) relaxation experiments [3–5].

1090-7807/$ - see front matter Ó 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jmr.2013.04.014
18 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
While sandstone and carbonate reservoirs often remain difficult
to interpret via NMR, shales present many additional challenges
when compared to conventional systems. Conventional reservoir
rocks are generally considered to have above 10% porosity and per-
meabilities greater than 1 millidarcy (mD). Shales typically have
only a few percent porosity and nano or picodarcy permeabilities.
This results in low signal-to-noise and samples require long run
times to obtain useful data. The pore sizes are also typically
in the nanometer range, leading to very short relaxation times. In
addition, a significant amount of the porosity in shales resides
in organic phases [6], giving rise to the possibility of homonuclear
dipolar coupling between fluids present and the organic matrix. In
contrast, the majority of dipolar interactions in conventional reser-
voirs arise from heteronuclear dipolar coupling between fluid mol-
ecules and paramagnetic impurities on the pore surface [7]. The
organic materials themselves may contain a significant quantity
of hydrogen. While kerogen has proton relaxation times that are
too short to be measured by many NMR systems, bitumen has
relaxation times long enough to be measured by most NMR
instruments.
For many of the shales, the T2 relaxation time constants are ex-
tremely short and push the limits of technical capabilities of low-
field NMR equipment. In addition, due to the high number of
hydrogen-bearing constituents present in shales, interpretation of
the shale system from a single type of measurement is challenging.
This has led to increased use of T1 measurements in shale charac-
terization. The reasoning behind this is that, while engineering
equipment that can measure shorter T2 values is a significant chal-
lenge, physics dictates T1 relaxation must be longer than or equal
to T2 and, as such, is potentially easier to measure. However, unex-
pectedly, the amount of signal measured from the T1 experiments
is often significantly less than what is determined by T2 experi-
ments. This discrepancy comes from the methods used to acquire
the T1 results and is discussed in more detail in subsequent sec-
tions. As such, the basic T1 and T2 measurements are often inade-
quate to confidently characterize these samples and new NMR
techniques are required to better understand and describe shale
samples.
We present two new pulse sequences to address the added
challenges of NMR in shales, the T1-solid echo and the T1–T2 solid
echo correlation. For this article, we apply these techniques to
characterize organic solids present in oil shales. While the NMR
techniques described here do not reveal detailed chemical compo-
sition information that other spectroscopic methods provide, the
techniques can be used to identify hydrogen-bearing constituents
in complex organic-rich rocks and can be useful to quantify these
constituents. We expect that these new NMR pulse sequences
can be applied to characterize other unconventional resources such
as tight-gas sands, oil-bearing shales, coalbed methane, gas
hydrates, and tar sands, but their treatment is beyond the scope
of this study.
2. Background
2.1. Shale resources
In many cases, the term shale is a misnomer in the geological
sense. The most common definition is that shales are clay-rich
rocks containing silt-sized particles of other minerals. However,
in the context of the petroleum industry, the term shale gets used
to describe any rock containing clay-sized to silt-sized particles.
Some of these may be true argillaceous, clay-rich shales while
many others are predominantly composed of fine-grained carbon-
ates or silt-sized silicate particles. Shales also may contain signifi-
cant quantities of organic matter, ranging from trace amounts to as
much as 70% by volume for some of the richest oil shales. This or-
ganic matter takes two forms, which are operationally defined by
their extractability with organic solvents. One form, kerogen, is a
geopolymer formed during diagenesis, a process in which organic
matter from biological sources (bacteria, algae, plants) is altered
by the heat and pressure of burial and compaction [1,8]. It has
no fixed molecular structure and is insoluble in solvents like chlo-
roform. Much work has been performed, both with solid state NMR
[9,10] and other techniques, to elucidate its different structural
characteristics. Kerogen may be hydrogen-rich or hydrogen-poor
depending on its depositional origin and thermal maturity. Bitu-
men is the other form of organic matter present in shales. Some
bitumen is present in source rocks before catagenesis and more
is generated as an intermediate phase during the transformation
of kerogen to oil and gas. Unlike kerogen, bitumen is soluble in
many organic solvents.
This study focuses on characterizing the solid organic matter in
oil shales to test the T1-solid echo and T1–T2 solid echo correlation
techniques. Oil shales have traditionally held a niche market in the
oil industry and, due to their name, are frequently confused with
oil-bearing shales. Shale reservoirs can be sorted into three main
types depending on the nature of the resource present: (1) oil
shales (e.g., Eocene Green River Formation), (2) oil-bearing shales
(e.g., Devonian–Mississippian Bakken Formation) and (3) tight-
gas shales (e.g., Mississippian Barnett Formation). Oil shales are
immature source rocks that have not been exposed to the neces-
sary temperature, pressure and time to convert kerogen to oil
and gas. These resources require heating to high temperatures
(350–600 °C) in the absence of oxygen (e.g., retorting) to produce
liquid and gaseous petroleum products. In contrast, shales that
have experienced high enough temperatures for sufficient periods
of time to produce liquid petroleum are referred to as oil-bearing
shales or tight-oil shales. Finally, at higher temperatures and long-
er heating times, the oil cracks further and the resource will con-
tain mostly gas. The transition between oil-bearing shale and
tight-gas shale is not abrupt and there is a transition zone where
both resources are present in significant amounts.
In an effort to better understand the oil generation process,
these natural oil-generating processes are mimicked in the labora-
tory on oil shale samples through artificial maturation methods.
This allows controlled experimentation upon homogenous rock
samples, avoiding the complications of variable mineralogy and or-
ganic content that occur with samples of differing maturity from
naturally-matured systems. Because these immature oil shale sam-
ples contain no liquid hydrocarbons or free water, they are excel-
lent test samples for our methodology on organic solids and
semi-solids. While we expect differences in the NMR response
from organic matter in samples containing liquids in the pore
space, experimentation on oil shales allows us to understand the
relaxation behavior of the organic solids alone before moving onto
more complex systems.
2.2. NMR theory
NMR has been used extensively to characterize porous materi-
als [11–17]. In particular, NMR has been used by the petroleum
industry since shortly after its discovery to assess fluid-saturated
porosity and pore size distributions [18,19]. The Carr–Purcell–Mei-
boom–Gill (CPMG) transverse relaxation measurement has been
the NMR standard for the oil industry. This measurement is fast,
robust, and can be performed even under the demanding condi-
tions present in the borehole [20]. The resulting relaxation time
distribution can be correlated with the distribution of pore sizes
present in the system. When low-viscosity fluids are placed in a
porous material, the effect on the measured T2 is described by
the equation [21]:
 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
1 1 S Dc2 G2 T 2E
¼ þ q2 þ ð1Þ
T 2 T 2Bulk V 12
where q2 is the surface relaxivity of the pore surface for T2, S is the
pore surface area, V the volume of the pores, D is the diffusion coef-
ficient of the fluid, c is the gyromagnetic ratio, G is the magnetic
field gradient and TE is the echo spacing. In most measurements, a
short echo spacing is chosen to avoid the influence of diffusion
through internal gradients on the signal. The T1 response of low vis-
cosity fluids in porous materials is similar, though unaffected by the
presence of internal gradients.
1 1 S measurement with a solid echo, Fig. 1c. Solid echoes have been
¼ þ q1 ð2Þ
T 1 T 1Bulk V
where q1 is the surface relaxivity of the pore surface for T1. While
the presence of multiple fluid types can make interpretation more
difficult, NMR techniques have been developed to take advantage
of diffusivity differences between fluid types to separate out the sig-
nals from different fluids [22].
In contrast, the organic solids present in shale samples will not
relax via the mechanisms described by Eqs. (1) and (2). Instead, the
high viscosity of the organic phases will cause interactions from re-
stricted motion to dominate the relaxation processes. Because of
this, pore surface relaxivities [23] or internal gradients [24] from
paramagnetic impurities in the sample will not influence the relax-
ation time of the organic matter. However, given the well-coupled
states of the spins, the possibility of spin diffusion to paramagnetic
impurities in shale is a potential source of additional relaxation.
For T1 in organic solids, the relaxation times will be long be-
cause the frequency of fluctuations in solids are inefficient at trans-
ferring energy to the environment while the T2 relaxation times
will be shorter due to the strong intramolecular dipolar coupling
that quickly dephases the spins. This leads to problems when
attempting to measure T1 in shales. The inversion recovery meth-
od, shown in Fig. 1a, is the most commonly used pulse sequence
for T1 measurement. Traditionally, the measurement is performed
by applying a 180° pulse to invert the magnetization, followed by a
90° pulse to place the magnetization in the transverse plane fol-
lowed by signal acquisition by detecting the resulting free induc-
tion decay (FID). For analysis of most conventional samples, this
method of measuring T1 appears to be adequate.
However, because of dipolar coupling, many shale samples have
very short T 2 transverse magnetic relaxation times such that a sig-
nificant portion of the FID signal has decayed away during the dead
time of the receiver after the 90° pulse. Furthermore, damping is
present in most low-field systems to decrease the amount of ring-
ing in the coil after a pulse. This damping typically decreases the
ringing such that it is a negligible contribution to the overall signal,
but, in shales, the very low porosity can lead to signals that are
comparable in intensity to the coil ringing. Therefore, longer dead
times may be needed to adequately damp the ringing when exam-
ining these types of samples, leading to even further loss of signal
Fig. 1. (a) Standard inversion recovery, (b) inversion recovery with spin echo,
(c) inversion recovery with solid echo, (d) inversion recovery with solid echo train.
19
intensity. Even with longer dead times, some coil ringing may be
measured and will manifest as a DC baseline in the measurement.
In these samples, measuring the intensity with a spin echo, Fig. 1b,
allows the signal to be recovered and avoids issues associated with
longer dead times, providing the desired results without artifacts.
Unfortunately, the spin echo only recovers magnetization lost
due to chemical shift anisotropy, underlying magnetic field inho-
mogeneity, and heteronuclear dipolar coupling. When homonu-
clear dipolar coupling is present, this signal intensity will still be
lost in a T1 measurement.
These issues are resolved by combining the inversion recovery
used to characterize a wide variety of samples ranging from rubber
[25,26] to food stuffs [27,28] to hydrogels [29,30]. Some work has
been done to perform a single-shot T1 from a solid echo [31], but to
the authors’ knowledge, this is the first instance of an inversion
recovery measured from a solid echo. For systems containing het-
eronuclear and homonuclear dipolar coupling, the solid echo will
refocus both types of couplings provided T 2  s. For low frequen-
cies, the contribution of chemical shift to T 2 can be neglected. Of
greater concern will be the homogeneity of the magnetic field,
the radiofrequency (rf) pulse, and the internal gradients present
in the sample. Therefore, the assumption T 2  s needs to be trea-
ted with caution. For samples containing hydrogen in both liquid
and solid phases, it is recommended that the T 2 of the liquid com-
ponents be estimated before applying these techniques. Addition-
ally, the optimal s length for producing a solid echo from spins
undergoing homonuclear dipolar coupling relates to the strength
of that coupling; stronger couplings need shorter s values. For sol-
ids, dipolar-coupling strength can be on the order of 10’s of kHz,
and therefore, a short s is necessary to adequately recover their
contribution. This may impose a limit on the size of probe that
can be used, as the minimum possible s that can be achieved typ-
ically increases with probe size. Similarly, rf homogeneity also
tends to decrease with increased probe size. These factors may lim-
it the use of the technique on samples at pressures and tempera-
tures relevant to in situ reservoir conditions, which often need
larger probes to accommodate the sample cell. Sample size may
also be restricted by the field homogeneity of the magnet. The rf
and magnetic field requirements may also hinder the use of the
techniques downhole by NMR logging tools. In addition, the solid
echo only completely refocuses the homonuclear dipolar coupling
for isolated spin pairs. The more coupled a system is, the less effi-
cient the solid echo will be at refocusing the magnetization.
This change in methodology also naturally lends itself to exten-
sion to a second dimension. Just as spin echoes can be combined to
produce a CPMG train [32,33], solid echoes can be combined to
produce a solid echo train, Fig. 1d. Several experiments were per-
formed to combine the T1 measurement with a solid echo train
to produce T1–T2 correlation data sets. Also, performing a solid
echo train along with a regular CPMG could provide additional
information regarding the amount and nature of solids within a
sample. Polymer [34,35] and materials sciences [36,37] have uti-
lized this technique previously, but it has thus far not been applied
to geological samples.
3. Methods
The oil shale samples originated from the Eocene Green River
Formation and are rich in type I kerogen. Two different shales were
investigated, both from the Piceance Basin in northwestern Colo-
rado; Anvil Points Mine (APM) Mahogany zone oil shale and illitic
oil shale from the Garden Gulch Member (GGM) R1 zone. The APM
shale is typical of Green River dolomitic marlstones. The GGM
shale is from the deeper zones of the Green River Formation and
20 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28

Fig. 2. (a) Standard inversion recovery and solid echo T1 measurements on decane,
Fig. 3. (a) Raw data from T1 measured via FID, spin echo, and solid echo on a GGM
(b) standard inversion recovery and solid echo T1 measurements on reservoir
sample heated for 264 h, (b) inverted data from T1 measured via FID, spin echo, and
sandstone, (c) standard inversion recovery and solid echo T1 measurements on the
solid echo on a GGM sample heated for 264 h.
Bakken Formation sample.

contains a significant amount of illite and illite–smectite rich layer Table 1

clays, approximately 30% as measured by XRD. Samples of the Simulated relaxation decays and inverted signal intensities.

Green River shales were crushed, sieved to 8 mesh and subjected T1 (ls) T2 (ls) Inverted signal intensity
to artificial maturation by pyrolysis using a laboratory process de- Simulation 1 1,000,000 50 1.062
signed to mimic in situ retorting of oil shale to convert kerogen to Simulation 2 500 50 1.009
oil and gas [38]. Crushing of the sample allows for homogenization Simulation 3 500 20 0.977
between sets; shales are extremely heterogeneous and obtaining Simulation 4 100,000 20 1.033

similar properties from even plugs taken right next to each other
is not assured. Aliquots (100 g) of the APM and GGM shales were
heated to 360 °C from 6 to 288 h. APM samples were heated for
6, 24, 72, and 288 h respectively, and samples of GGM were heated
for 24, 72, 120, and 264 h. All samples were processed and stored
dry, however, no attempt was made to remove mineral-bound
water in the raw or pyrolyzed shales. Due to the method used to
artificially mature these samples, it is not expected that any appre-
ciable quantity of liquid hydrocarbon or water remains in the pore
space of the pyrolyzed shales.
While we are interested in identifying and measuring organic
solids, several other types of sample measurements were taken
to provide verification and confidence in the NMR techniques. In
order to verify the methods do not introduce artifacts in liquids,
NMR measurements were performed on a 5-mL aliquot of decane
to determine T1 relaxation times using the FID and solid echo
one-dimensional methods, and spin echo and solid echo trains
for two dimensional T1–T2 correlations. Also, a conventional reser-
voir sandstone and a sample from the middle part of the Bakken
Formation, which both had been cleaned and resaturated with syn-
thetic formation brine, were used to test the response between T1
measured using the standard inversion recovery and the solid echo
method. While the pore sizes in the Bakken sample are small and
the sample has low permeability, it is a clean carbonate with very
little clay or organic matter and as such, was expected to have little
signal contribution from homonuclear dipolar coupling. Naphtha-
lene and low-density polyethylene (LDPE) beads were used as solid
standards for evaluating the T1–T2 correlation technique responses
 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
Fig. 4. (a) Simulated data 1, (b) simulated data 2, (c) simulated data 3, and (d) simulated data 4.
on solid organic matter phases comparable to those in Green River
Formation kerogen.
NMR measurements were performed using a 2-MHz Magritek
Rock core analyzer using a 35-mm probe optimized for shale re-
sults. For the NMR measurements, the crushed samples were
placed in 1-in. diameter test tubes, which were filled to a height
of 2 in. This corresponds to the maximum sample volume for the
probe. One-dimensional results were inverted using a Butler Reed
Dawson inversion [39]. Two-dimensional results were inverted
using a maximum-entropy method [40]. All echoes were per-
formed with a 30 ls s value, the minimum value possible with this
equipment. To evaluate the response of the two-dimensional
inversion at very short relaxation times, a set of T1–T2 simulated
relaxation measurements using these parameters were created
and then inverted. Measurements of the FID were performed with
20 ls damping. Repetition time for all measurements was per-
formed with a 5-s wait time, except the naphthalene, which had
a 20-s wait time.
In addition to NMR, samples also underwent Rock Eval pro-
grammed pyrolysis [8,38] in prior studies. This approach was used
to estimate the amount of kerogen and bitumen present in the raw
and pyrolyzed oil shales and the results of these experiments have
been previously published [38].
4. Results
4.1. One-dimensional measurements
The T1 measurements on decane yielded nearly identical results
for both the inversion recovery and solid echo pulse sequences,
Fig. 2a. There was only a 0.8% difference in the integrated signal
intensity between the two methods. This is within expected
21
experimental tolerances. The measurements upon the cleaned,
brine-saturated reservoir rocks, Fig. 2b and c, yielded similar re-
sults, with minor differences that were most significant at short-
relaxation times. The sandstone produced 5% higher signal inten-
sity from the solid echo measurement than the T1 measured from
a spin echo. The sandstone is known to contain approximately 3–
8% clay, so the results are consistent with expected behavior. While
normal T1 and T2 measurements can measure clay-bound water, it
is not surprising that additional relaxation might occur due to homo-
nuclear dipolar coupling from restricted motion of water in the clay.
In addition, conventional reservoirs often contain tiny amounts of
organic matter which could lead to the additional signal observed.
The Bakken Formation sample showed consistent results be-
tween the methods with approximately 2% difference in signal
intensity. While the core sample is tight, with a permeability less
than one millidarcy and very small pore sizes, there was only a
small difference between the results for the different T1 methods.
These results provide confidence that the solid echo measurement
does not introduce unusual artifacts into the measurement on
samples without significant homonuclear dipolar coupling. Note,
as s duration is increased, discrepancy between the solid echo
measurements and the other techniques may arise.
The three different T1 methodologies were repeated multiple
times (n = 4) for several samples to determine average error values
for each pulse sequence. The results from a sample of the GGM
shale which had undergone artificial maturation at 360 °C for
264 h are presented in Fig. 3a. Sixty-four scans were performed
for each T1 point for all measurements. Receiver gain was kept con-
stant throughout all measurements.
The ideal T1 measurement produces a clean s-shaped curve on a
log scale, starting at a negative value, progressing through zero,
and ending at a positive value similar to the initial negative inten-
sity. While the standard inversion recovery measurement showed
22 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28

Fig. 5. (a) T1–T2 correlation measurement on decane using a spin echo train, (b) T1–T2 correlation measurement on decane using a solid echo train, (c) T1–T2 correlation
measurement on naphthalene using a spin echo train, (d) T1–T2 correlation measurement on naphthalene using a solid echo train, (e) T1–T2 correlation measurement on LDPE
beads using a spin echo train, (f) T1–T2 correlation measurement on LDPE beads using a solid echo train.

the poorest repeatability, overall repeatability was good for all
three methods. The average standard deviation for the signal from
the T1 FID measurement was 0.59 nV, whereas the average stan-
dard deviation for the T1 experiments using the spin echo and solid
echo methods were 0.44 nV and 0.46 nV, respectively. The T1 mea-
sured from the FID was of poor quality, as the signal never crossed
into the negative and showed significant baseline offset despite the
long damping times used. The T1 measured from a spin echo
showed more of the classic s-shape expected for T1 experiments.
The T1 measured using the solid echo method produced more sig-
nal than the spin echo measurement, indicating some signal loss
due to homonuclear dipolar coupling. While the solid echo pro-
duced more signal than the spin echo, the measured negative val-
ues at short times were not equivalent to the positive values
measured at long times, indicating the measurement was still
not fully capturing the signal at short times. We speculate that
measurement at an even shorter s may improve determination of
the very short T1 values. However, it could be that the lost signal
is undergoing a significant number of homonuclear interactions
such that the solid echo is not as effective at recovering that signal
as it is for more isolated spin pairs. Measurements made on other
samples showed similar behavior between the three pulse
sequences.
The inverted results, Fig. 3b, show distinct differences between
the measurement methods. When corrected for baseline offset, the
measurement from the inversion recovery produced results similar
in shape to the other two methods, but the intensity was signifi-
cantly lower than what was generated by the echo methods,
approximately 45% less than the T1 from the spin echo measure-
ment and 56% less than the solid echo T1. The solid echo measure-
ment showed additional signal intensity at lower T1 times. The
total signal intensity from the solid echo was approximately 22%
greater than that of the T1 spin echo measurement. The spin echo
T1 results at short time consists of two peaks between 0.1 ms
 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
Fig. 6. Anvil point mine spin echo T1–T2 correlation, (a) raw shale, (b) 360 °C 6-h ISS, (c) 360 °C 24-h ISS, (d) 360 °C 72-h ISS, and (e) 360 °C 288-h ISS.
and 100 ms. The solid echo T1 results appear to consist of three
overlapping peaks. To gain better resolution of the spectra, we
introduced a second dimension to correlate the T1–T2 relaxation
behavior.
4.2. Two-dimensional measurements
The stability of the two-dimensional inverse Laplace transform
at short relaxation times is often a concern. To test its behavior,
simulated decays were produced with relaxation times reflecting
those seen in the real measurements. Relaxation values are shown
in Table 1. The intensity of each of the decays was set to one to al-
low for ease of comparison between the simulations. The resulting
integrated intensities from the inverted results are also shown in
Table 1. The inverted results of simulated decays reproduced the
relaxation times remarkably well, Fig. 4, despite the T2 times being
below the echo spacing of the measurement. For simulated sam-
ples 3 and 4, the peaks had a tendency to hug the boundary. Sim-
ulations for T2 values above 60 ls had 1% or less deviation in
23
inverted intensity compared to simulated intensity and had no dis-
tortion of the peak locations. The results add confidence to the
resulting short relaxation times seen in the experimental results.
Experimental validation measurements were also performed for
the two-dimensional data sets. The T1–T2 correlation results for
decane, Fig. 5a, showed only minor differences between the two
pulse sequences. The peak location was unchanged and intensity
differences between the two measurements were less than 1%. This
gives us confidence that the two-dimensional T1–T2 solid echo
measurement also does not introduce artifacts compared to the
spin echo method in systems not containing significant homonu-
clear dipolar coupling.
The naphthalene T1–T2 correlations, Fig. 5c, produced a strong
signal at very short T2 and long T1 times characteristic of solid sam-
ples [41]. Notably, the T1 was longer than any other measured T1 in
our sample set. We believe this may arise from ring-stacking of the
naphthalene molecules, leading to a more rigid structure than the
other measured systems. In addition, an unexpected peak appeared
at longer T2 times. This was attributed to naphthalene sublimating
24 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28

Fig. 7. Anvil point mine solid echo T1–T2 correlation, (a) raw shale, (b) 360 °C 6-h ISS, (c) 360 °C 24-h ISS, (d) 360 °C 72-h ISS, (e) 360 °C 288-h ISS.

during the measurement process. The resulting signal intensity

Table 2 from the solid echo was approximately three times the signal
Anvil point mahogany total integrated signal intensity comparison between spin echo intensity of the spin echo. However, precise comparison was hin-
and solid echo measurements. dered by the effects of sublimation.
Raw 6h 24 h 72 h 288 h The LDPE beads, Fig. 5e, produced a stable T1–T2 correlation re-
sult. We speculate the multiple peaks arise from chains of differing
Spin echo 5.10 13.90 11.64 9.42 1.84
Solid echo 11.79 15.81 12.32 11.81 2.48 lengths or from different structural domains, such as branched
chains or semi-crystalline structures. FTIR analysis of the material
indicated oxidation of the surface layers in the form of ester bands
(not shown). The signal intensity from the solid echo was nearly
twice that of the spin echo measurement. While both samples dis-
Table 3 play the anticipated long T1 and short T2 behavior of solids, we be-
Anvil point mahogany solid echo peak intensity measurements as a function of
lieve the LDPE beads to be a better analogue for most oil shale
maturation time.
kerogens than naphthalene. These results also provide confidence
Raw 6h 24 h 72 h 288 h in the veracity of the short T2 values we observe in the results
Peak A 5.07 2.51 1.58 1.34 0.47 for the oil shale samples.
Peak B 3.31 5.39 3.83 1.69 0.54 The results for the oil shale samples from a standard spin
Peak C 0.00 6.08 4.65 3.10 0.38 echo T1–T2 correlation provide significant improvement for
Peak D 0.00 0.39 1.03 3.80 0.19
interpretation of hydrogen-bearing constituents compared to the
 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
Fig. 8. Garden Gulch Member spin echo T1–T2 correlation, (a) raw shale, (b) 360 °C 24-h ISS, (c) 360 °C 72-h ISS, (d) 360 °C 120-h ISS, and (e) 360 °C 264-h ISS.
one-dimensional case. The signal is observed to be far from T1–T2
parity, indicating that it is generated from highly viscous or solid
components. This agrees with previously published characteriza-
tion of these samples from programmed pyrolysis; while a small
amount of bitumen is present in the raw shale samples, the major-
ity of the hydrogen resides in solid kerogen [38]. Based on the re-
sults, we are confident that the resulting signal is from kerogen. To
the authors’ knowledge, this is the first low-field NMR measure-
ment of kerogen-associated hydrogen. However, it is likely that
only a portion of the overall kerogen signal is being observed; it
is anticipated that there exists still more signal at T2 relaxation
times not currently accessible due to present equipment
limitations.
The solid echo T1–T2 correlation for the raw APM shale, Fig. 7a,
shows several differences from the spin echo T1–T2 correlation
measurement, Fig. 6a. The signal intensity of the solid echo T1–T2
measurement is twice that of the spin echo T1–T2. Peaks I and II
gain approximately 50% and 35% in signal intensity respectively.
Because the solid echo is most efficient at refocusing isolated spin
25
pairs, the differences in intensity between the spin echo and solid
echo may yield information regarding the chemical structure of the
components. Further work is necessary to correlate these relaxa-
tion times to spectroscopic data for more definitive identification.
Peak I shifts to slightly longer T2 times, while Peak II T2 relaxation
times become longer by two orders of magnitude. This indicates
the majority of relaxation of Peak II comes from homonuclear dipo-
lar coupling. The largest signal intensity increase comes from the
addition of the third peak with a very short T2 time. This peak is
attributed to portions of the kerogen undergoing significant homo-
nuclear interactions such that the T2 is not measurable during a
standard spin echo T1–T2 correlation.
Comparison of total signal intensities for the two types of mea-
surements for the APM samples are shown in Table 2. For the raw
sample, the vast majority of the signal corresponds to relaxation
times well away from the T1–T2 parity line. As the samples undergo
artificial maturation, the kerogen decomposes into bitumen,
Figs. 6b and c and 7b and c. The bitumen is viscous, but more li-
quid-like than kerogen and the transformation is reflected in the
26 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28

Fig. 9. Garden Gulch Member solid echo T1–T2 correlation, (a) raw shale, (b) 360 °C 24-h ISS, (c) 360 °C 72-h ISS, (d) 360 °C 120-h ISS, (e) 360 °C 264-h ISS.

Table 4
Garden Gulch Member total signal intensity comparison between spin echo and solid
the T1–T2 parity line. Seventy-two hours represents peak bitumen
echo measurements.
generation under these conditions for this sample [38]. The expul-
Raw 24 h 72 h 120 h 264 h sion of oil and gas leads to loss of hydrogen from the system. This is
Spin echo 17.76 14.67 12.39 9.24 8.77 reflected in the reduced overall intensity determined by both types
Solid echo 24.33 19.99 13.16 10.40 9.68 of T1–T2 correlation experiments. At longer heating times, much of
the bitumen has partially cracked to yield oil and gas [38], leading
to an increase in bitumen viscosity, as reflected in the T1–T2 corre-
Table 5 lation times, Figs. 6e and 7e. After seventy-two hours maturation,
Garden Gulch Member solid echo peak intensity measurements as a function of the T2 peak shifts to shorter times, indicating an increase in the
maturation time. stiffness of the material.
Raw 24 h 72 h 120 h 264 h Comparing the total signal intensity between the solid and spin
Peak A 6.26 1.44 0.91 0.74 0.88
echo measurements, the greatest difference between measure-
Peak B 4.75 5.05 2.55 1.73 2.33 ments is seen in the raw sample results. There, most of the hydro-
Peak C 0.00 6.68 3.62 2.49 2.71 gen resides in the solid phase. As the samples are thermally
Peak D 0.00 3.51 3.04 1.87 0.47 matured and increasing amounts of bitumen are produced, the dif-
Peak E 8.72 2.09 1.68 1.81 1.37
ference in intensity between the two measurements decreases. Fi-
nally, as the less viscous bitumen is cracked and chars, leaving
peak locations in the plots. With longer heating times, Figs. 6d and behind a stiffer, more solid organic phase, the ratio between the so-
7d, the signal shifts to longer T2 relaxation times and approaches lid echo and spin echo signal intensity increases. This suggests that
 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
the ratio of intensities between the two measurements can poten-
tially be used as an indicator of component stiffness.
Both the spin echo and solid echo T1–T2 correlation measure-
ments allow for qualitative observation of the artificial maturation
process, but the solid echo T1–T2 correlation produces results with
more stable peak configurations between the different pyrolysis
times, making interpretation easier. We divide the signal into four
main peaks, A, B, C, and D, labeled in Fig. 7d, and integrated the
intensity of each peak. It should be noted that peaks may, but
not necessarily, belong to separate constituents in a sample. In-
verse Laplace inversion methods have a tendency to ‘‘pearl’’, where
a continuous distribution is broken into separate peaks. This arti-
fact can be useful, acting to histogram intensity in the correlation
spectrum, but needs to be kept in mind in terms of the physical
interpretation of the results. Signal intensities, shown in Table 3,
were normalized for sample weight, number of scans, and receiver
gain. The peak at very short T2 time, peak A, which we speculate
belongs to kerogen, consistently decreases as the shales are ex-
posed to pyrolysis conditions for longer periods of time. The inten-
sity of peaks B, C, and D first increased and then decreased with
increased heating time. The change in intensity is in general agree-
ment with the previously published measurements of kerogen and
bitumen content of these samples from bulk-analysis and pro-
grammed pyrolysis [38]. Kerogen content is at a maximum for
raw shales and consistently decreases with increased maturation.
Bitumen content is low in the raw shale, increases significantly
upon heating, and begins to decrease at 72 h under ISS conditions.
The GGM raw shale results, Figs. 8a and 9a, show similar relax-
ation time distributions as the APM raw shale, with the exception
of an additional intense peak at approximately T2 = 104 s and
T1 = 103 s. This peak may arise from water molecules trapped in
empty potassium sites between the layers of illite.
Like the APM shale, while the spin echo T1–T2 correlation al-
lowed for a qualitative interpretation, the results from the GGM
shale using the T1–T2 solid echo correlation show a more consis-
tent, stable peak configuration throughout the artificial maturation
process. Given the more complicated signal configuration, confi-
dently determining the relationship between the spin and solid
echo T1–T2 peaks for the GGM shale is more challenging than for
the APM shale. However, it appears the peak attributed to water
associated with illite (Peak E) shows less increase in intensity be-
tween the spin and solid echo measurements, from 15% to 20%,
than the portions of the signal attributed to organic matter, which
showed nearly a 50% increase. Changes in the intensity of different
peaks between spin and solid echo experiments could help identify
sample constituents, though more extensive testing in conjunction
with other geochemical analyses is required.
Unlike the APM shale, which displayed an initial increase in to-
tal signal intensity during pyrolysis, the GGM shale shows a de-
crease in total intensity throughout, Table 4. This difference is
attributed to the high concentration of illite in the GGM shale
(approximately 30 wt.%). While the components of the signal from
bitumen initially increased, Table 5, again reflecting that the com-
plete kerogen signal is not being measured, the large peak from il-
lite decreases with increased heating time. This intensity decrease
displays an asymptotic behavior; there is a significant decrease in
intensity upon initial heating and slower decreases at longer heat-
ing times. This is consistent with results of other researchers, who
showed that heating illite to temperatures above 250 °C was suffi-
cient to start removing the interlayer water [42]. For the two GGM
samples that underwent pyrolysis for longer periods of time, (120
and 264 h), we see a similar shift to shorter T2 relaxation times as
the corresponding APM sample (288 h). Bitumen content has de-
creased significantly in the 120- and 264-h GGM samples as much
of the bitumen has been cracked to oil and gas. The GGM samples
contained a significantly greater signal compared to the APM
27
samples, even after 264 h of maturation. This agrees with previ-
ously observed behavior in clay-rich source rocks [43], which are
known to retain more generated petroleum products than samples
with lower clay content. Alternatively, some of this additional sig-
nal could arise from remaining water in the clay.
These results indicate that comparison of measurements made
between standard spin echo techniques and the new solid echo
techniques presented can potentially be used to help identify and
characterize highly viscous and solid organic components in shale
systems. However, we anticipate that for shale samples containing
both significant quantities of organic matter and low viscosity liq-
uids, such as oil and water, the NMR response will be more compli-
cated than a simple summation of the relaxations from the solid
and liquid components. Significant interplay between solids and
liquids may occur due to mechanisms such as spin diffusion,
homonuclear dipolar coupling between the organic solids and
petroleum, and increased petroleum residence time on organic
pore surfaces. The solid–liquid behavior may not be a one-way
interaction of the matrix influencing the liquid relaxation times
like in conventional hydrocarbon resources; the liquids may also
influence the relaxation behavior of the organic solids in the pore
matrix for shales. New methods of artificial maturation have been
developed for core plugs under confinement, better imitating the
maturation processes in situ and allowing the samples to retain
some of the produced petroleum. Research using spin and solid
echo techniques on both natural oil-bearing shales as well as arti-
ficially matured core plugs are underway to better understand
these dynamics.
5. Conclusions
Shale samples show significant deviation in behavior from the
standard interpretation of conventional fluid-saturated reservoir
rocks where relaxation time is correlated with pore size and sur-
face relaxation is dominated by heteronuclear dipolar interactions
with paramagnetic impurities. While there still remains significant
work to be done to better understand the NMR response from the
broad range of shales, improved instrumentation and the addition
of solid echo-based techniques provide another tool for identifying
and studying different constituents in shale samples. By perform-
ing experiments using both the standard spin echo and solid echo
techniques, it appears possible to obtain more complete informa-
tion on the hydrogen-bearing constituents present in shales. With
a short s, the response from low viscosity liquids appears to be un-
changed between the spin and solid echo experiments while signif-
icant differences are seen in samples containing highly viscous and
solid organic matter. The ratio of intensities between the two mea-
surements could provide structural information on sample constit-
uents. Measuring the NMR response for a range of solid echo
spacings may also yield additional useful information. Results sug-
gest that for samples containing a significant amount of bitumen or
kerogen that measurement of T1 alone will be insufficient, particu-
larly using the inversion recovery measured from an FID, and a two
dimensional experiment provides more information for system
interpretation. Although this study focused on oil shales, the
techniques applied have a wider range of potential applications,
particularly to geologic samples related to other unconventional
petroleum resources.
Acknowledgments
The authors thank Michael Lewan, Tim Ruble, and Dick Drozd
for helpful discussion on general issues related to shales, Andrew
Coy and Christopher Laughrey for manuscript review, Alan
Burnham for the Garden Gulch samples; Lauren Burcaw for LaTeX
28 K.E. Washburn, J.E. Birdwell / Journal of Magnetic Resonance 233 (2013) 17–28
assistance, and Max Goldstein for assistance in running samples.
Any use of trade, product, or firm names is for descriptive purposes
only and does not imply endorsement by the U.S. Government.
References
[1] B. Tissot, D. Welte, Petroleum Formation and Occurrence, Springer Verlag,
Berlin, 1984.
[2] D. Luffel, F. Guidry, New core analysis methods for measuring reservoir rock
properties of Devonian shale, J. Petrol. Technol. 44 (1992) 1184–1190.
[3] C. Sondergeld, R. Ambrose, C. Rai, J. Moncrieff, Laboratory NMR measurements
on methane saturated Barnett shale samples, SPE Proc. (2010) 131771.
[4] R. Sigal, E. Odusina, Laboratory NMR measurements on methane saturated
Barnett shale samples, Petrophysics 52 (2011) 32–49.
[5] E. Odusina, C. Sondergeld, R. Ambrose, C. Rai, An NMR study of shale
wettability, SPE Proc. (2011) 147371.
[6] R. Loucks, R. Reed, S. Ruppel, D. Jarvie, Morphology, genesis, and distribution of
nanometer scale pores in silicious mudstones of the Mississippian Barnett
shale, J. Sediment. Res. 79 (2009) 848–861.
[7] R. Kleinberg, W. Kenyon, P. Mitra, Mechanism of NMR relaxation of fluids in
rock, J. Magn. Reson. 103 (1994) 206–214.
[8] M. Bordenave, Applied Petroleum Geochemistry, Editions Technip, Paris, 1993.
[9] U. Werner-Zwanziger, M.M.G. Lis, A. Schimmelmann, Thermal maturity of type
II kerogen from the New Albany shale assessed by 13c CP/MAS NMR, Solid
State Nucl. Magn. Reson. 27 (2007) 140–148.
[10] J. Mao, X. Fang, Y. Lan, A. Schimmelmann, M. Mastalerz, L. Xu, K. Schmidt-Rohr,
Chemical and nanometer-scale structure of kerogen and its change during
thermal maturation investigated by advanced solid-state 13C NMR
spectroscopy, Geochim. Cosmochim. Acta 74 (2010) 2110–2127.
[11] P. Callaghan, A. Coy, D. Macgowan, K. Packer, F. Zelya, Diffraction-like effects in
NMR diffusion studies of fluids in porous solids, Nature 351 (2009) 167–173.
[12] S. Stapf, B. Blumich, Multi-gradient pulse investigations of fluid transport in
porous media, Magn. Reson. Imag. 19 (2001) 385–389.
[13] Y. Song, Pore sizes and pore connectivity in rocks using the effect of internal
field, Magn. Reson. Imag. 19 (2001) 417–421.
[14] J. Seland, K. Washburn, H. Anderson, J. Krane, Correlations between diffusion,
internal magnetic field gradients, and transverse relaxation in porous systems
containing oil and water, Phys. Rev. E 70 (2004) 051305.
[15] K. Washburn, P. Callaghan, Tracking pore to pore exchange using relaxation
exchange spectroscopy, Phys. Rev. E 70 (2004) 051305.
[16] L. Burcaw, P. Callaghan, Observation of molecular migration in porous media
using 2d exchange spectroscopy in the inhomogeneous magnetic field, J.
Magn. Reson. 198 (2009) 167–173.
[17] J. Mitchel, T.C. Chandrasekera, L.F. Gladden, Obtaining true transverse
relaxation time distributions in high-field NMR measurements of saturated
porous media: removing the influence of internal gradients, J. Chem. Phys. 132
(2010) 244705.
[18] R.J.S. Brown, The earth’s-field NML development at Chevron, Concepts Magn.
Reson. 13 (2001) 344–367.
[19] J.S. Jackson, Los Alamos NMR well logging project, Concepts Magn. Reson. 13
(2001) 368–378.
[20] R. KLeinberg, NMR well logging at Schlumberger, Concepts Magn. Reson. 13
(2001) 396–403.
[21] R. Kleinberg, M. Horshfield, Transverse relaxation processes in porous
sedimentary rock, J. Magn. Reson. 88 (1990) 9–19.
[22] M. Hurlimann, L. Venkataramanan, C. Flaum, The diffusion spin relaxation
time distribution function as an experimental probe to characterize fluids in
porous media, J. Chem. Phys. 117 (2002) 10223–10232.
[23] J. Bryan, A. Kantzas, D. Moon, In situ viscosity of oil sands using low field NMR,
Can. Int. Petrol. Con. Proc. (2003).
[24] M. Hurlimann, Effective gradients in porous media due to susceptibility
differences, J. Magn. Reson. 131 (1998) 232–240.
[25] G. Zimmer, A. Guthausen, B. Blumich, Characterization of cross-link density in
technical elastomers by the NMR-mouse, Solid State Nucl. Magn. Reson. 12
(1998) 183–190.
[26] J. Perlo, F. Casanova, B. Blumich, Profiles with microscopic resolution by single-
sided NMR, J. Magn. Reson. 176 (2005) 64–70.
[27] A. Davenel, P. Marchal, Rapid moisture and fat determination by pulsed NMR
for monitoring drying and coating processes of extrudates, Int. J. Food Sci.
Technol. 30 (1995) 655–662.
[28] X. Zhang, M. Do, P. Hoobin, I. Burgar, The phase composition and molecular
motions of plasticized wheat gluten-based biodegradable polymer mate-
rials studied by solid-state NMR spectroscopy, Polymer 47 (2006) 5888–
5896.
[29] T. Shiga, K. Fukumori, Y. Hirose, Pulsed NMR study of the structure of
poly(vinyl alcohol)–poly(sodium acrylate) composite hydrogel, J. Polym. Sci.
32 (1994) 85–90.
[30] C. Zaino, Y. Zambito, G. Mollica, M. Geppi, M.F. Serafini, V. Carelli, G. Di Colo, A
novel polyelectrolyte complex (PEC) hydrogel for controlled drug delivery to
the distal intestine, Open Drug Deliv. J. 1 (2007) 68–75.
[31] D. Burum, D. Elleman, W. Rhim, New technique for single-scan T1
measurements using solid echoes, Rev. Sci. Instrum. 49 (1978) 140–148.
[32] H. Carr, R. Purcell, Effects of diffusion on free precession in nuclear magnetic
resonance experiments, Phys. Rev. 94 (1954) 630–638.
[33] S. Meiboom, D. Gill, Modified spin-echo method for measuring nuclear
relaxation times, Rev. Sci. 29 (1958) 688.
[34] K. Fujimoto, T. Nishi, R. Kado, Multiple-pulse nuclear magnetic resonance
experiments on some crystalline polymers, Polym. J. 3 (1972) 448–462.
[35] P. Sotta, C. Fulber, D.E. Demco, B. Blumich, H.W. Speiss, Effect of residual
dipolar interactions on the NMR relaxation in cross-linked elastomers,
Macromolecules 29 (1996) 6222–6230.
[36] H. Kimoto, C. Tanaka, M. Yaqinuma, E. Shinohara, A. Asano, T. Kurotsu, Pulsed
NMR study of the curing process of epoxy resin, Anal. Sci. 7 (2008) 915–
920.
[37] H. Tanaka, Study of chemical gelation dynamics of acrylamide in water by real-
time pulse magnetic resonance measurement, J. Chem. Phys. 89 (1988) 3363–
3373.
[38] J. Birdwell, T. Ruble, C. Laughrey, D. Roper, G. Walker, Differentiating organic
carbon residues in spent oil shale, in: Oil Shale Symposium Proceedings,
2011.
[39] J. Butler, J. Reeds, S. Dawson, Estimating solutions of a first kind integral
equations with non-negative constraints and optimal smoothing, SIAM J.
Numer. Anal. 18 (1981) 381–397.
[40] E. Chouzenoux, S. Moussaoui, J. Idier, F. Mariette, Efficient maximum entropy
reconstruction of nuclear magnetic resonance T1–T2 spectra, IEEE Trans. Signal
Process. 58 (2010) 6040–6051.
[41] N. Bloembergen, E.M. Purcel, R.V. Pound, Relaxation effects in nuclear
magnetic resonance absorption, Phys. Rev. 73 (1948) 679–712.
[42] R. Grim, W. Bradley, Investigation of the effect of heat on the clay minerals
illite and montmorillonite, J. Am. Ceram. Soc. 23 (1940) 242–248.
[43] P. Ungerer, State of the art research in kinetic modeling of oil formation and
expulsion, Org. Geochem. 16 (1990) 1–25.