A novel integrated AUTHORS

approach for chemofacies Junwen Peng ~ State Key Laboratory of

Petroleum Resources and Prospecting,
China University of Petroleum (Beijing),
characterization of Beijing, China; junwen.peng@cup.edu.cn;
junwen@utexas.edu
organic-rich mudrocks Junwen Peng is a lecturer at China University
of Petroleum (Beijing). He received his B.S.
Junwen Peng and Toti E. Larson degree in resource exploration engineering
(petroleum geology) from China University
of Geosciences (Wuhan) in 2013. In 2016,
he graduated from China University of
ABSTRACT Petroleum (Beijing) with an M.S. degree in
A novel integrated approach for chemofacies characterization of geological resources and geological
engineering (petroleum geology). He
organic-rich mudrocks was developed using principal compo-
obtained his Ph.D. in geology at The
nents analysis of 25 elements from core-based energy-dispersive University of Texas at Austin in 2021. His
x-ray fluorescence (ED-XRF) measurements and k-means cluster- current research interests include shale
ing. Using this approach, three chemofacies were identified that sedimentology, shale petrography, and
capture the spread of the geochemical data sets (5000 ED-XRF sedimentary geochemistry. He is the
measurements from three cores) of the organic-rich Cline Shale corresponding author for this paper.
in the Midland Basin: (1) oxic-suboxic detrital-enriched argilla- Toti E. Larson ~ Bureau of Economic
ceous mudrocks, (2) anoxic siliceous mudrocks, and (3) oxic- Geology (BEG), Jackson School of
suboxic intrabasinal carbonates. Chemofacies defined by the Geosciences, The University of Texas at
covariances of elemental concentrations can be correlated to Austin, Austin, Texas; toti.larson@beg.
depositional environments and primary grain assemblages in a utexas.edu
predictable way, which has significant implications for the evolu- Toti E. Larson is a research associate at the
tion of bulk rock properties, such as total organic carbon (TOC), Bureau of Economic Geology. He received
rock mechanical property, porosity, and permeability. The strati- his Ph.D. from the University of New Mexico
graphically thin anoxic siliceous mudrocks, which are also charac- with a focus on stable isotope and elemental
terized by the highest TOC concentrations, moderate to high geochemistry. His main area of research is
brittleness, and the highest porosity and permeability, are the the integration of geochemistry and
geological characterization to better
“sweet spot” for shale oil production in the Cline Shale. Elevated
understand mudrock systems.
TOC values of the anoxic siliceous mudrocks are most likely
caused by anoxic benthic conditions. This integrated approach for ACKNOWLEDGMENTS
chemofacies characterization of mudrocks is an important step to
fully use all the geochemical data obtained through high- This paper comprises parts of the Ph.D.
project of Junwen Peng at The University of
resolution ED-XRF analyses and provide an economic, efficient,
Texas at Austin and was supported by the
and nondestructive method to study core. State of Texas Advanced Resource Recovery
program at the BEG, the China Scholarship
Council (Grant No. 201606440062), and the
INTRODUCTION Geological Society of America Graduate
Student Research Grant (Grant No.
Deposition of deep-water (i.e., below storm-wave base) organic- 9244823). The Firewheel Energy LLC
rich mudrock has long been considered to be controlled by (Houston, Texas) and Devon Energy
Corporation (Oklahoma City, Oklahoma) are
thanked for donating cores used in this
Copyright ©2022. The American Association of Petroleum Geologists. All rights reserved.
study. The authors thank Patrick Smith at the
Manuscript received December 17, 2020; provisional acceptance April 9, 2021; revised manuscript
received April 28, 2021; final acceptance May 19, 2021.
BEG imaging laboratory for assistance during
DOI:10.1306/05112120210

AAPG Bulletin, v. 106, no. 2 (February 2022), pp. 437–460 437

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 scanning electron microscope sample
preparation, Ben Herrmann at Devon Energy
Corporation for providing several thin
sections, John Grillo at Premier Oil Field Labs
(Houston, Texas), and Evan Sivil at the BEG
Mudrock Systems Research Laboratory for
help and guidance during energy-dispersive
x-ray fluorescence analyses and calibration.
Stephen C. Ruppel, Kitty L. Milliken, Robert
W. Baumgardner, Scott Hamlin, Robert Reed,
Nathan Ivicic, and Brandon Williamson at
the BEG are thanked for their constructive
suggestions and assistance during this study.
The publication was authorized by the
director of the BEG, Jackson School of
Geosciences, The University of Texas at
Austin.
DATASHARE 145
Tables S1 and S2 are available in an
electronic version on the AAPG website
(www.aapg.org/datashare) as Datashare
145.
438 Approach for Mudrock Chemofacies Characterization
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pelagic suspension fallout in low-energy environments because of
the homogenous or structureless depositional textures (e.g.,
Scholle, 1971; Wynn et al., 2000). However, detailed process-
based studies in recent years suggest that a wide range of transpor-
tational and depositional processes, such as low-density turbidity
currents and debris flows, may be responsible for the deposition
of deep-water mudrock successions (e.g., Loucks and Ruppel,
2007; Boulesteix et al., 2019; Peng, 2021). Furthermore, the
addition of new petrographic descriptions (e.g., Milliken et al.,
2012; Alnahwi et al., 2018; Peng et al., 2020a, b), high-resolution
bulk geochemical characterization (e.g., Rowe et al., 2012;
Alnahwi and Loucks, 2019; Larson et al., 2019; Kabanov et al.,
2020a, b; Peng et al., 2021), and mechanical characterization
techniques (e.g., Zahm and Enderlin, 2010) in mudrock strata
indicates that these various properties of mudrocks can vary sig-
nificantly at multiple scales ranging from submillimeter laminae
to outcrops, demonstrating the heterogeneous character of
mudrocks. Understanding such heterogeneity is necessary to
delineate the “sweet spot” that is characterized by high total
organic carbon (TOC) and good reservoir properties (high poros-
ity, high permeability, and high content of “brittle minerals”
imparting rigid mechanical properties to the rock), which is
essential for industrial unconventional resources exploration.
Characterization of mudrocks remains hindered mainly by
the required high-resolution petrographic description techniques,
petrophysical detection techniques, or rock mechanical property
analysis, which are extremely time consuming and uneconomic.
Moreover, these traditional laboratory-derived analyses require a
specific size and condition of each mudrock sample, which is
another obstacle to applying those methods at a scale that can
adequately capture the heterogeneity in mudrock successions
with limited samples. Thus, these laboratory-derived methods are
usually impractical to do with the large quantity of samples
required in industrial exploration (e.g., more than thousands).
This study aims to provide a cost-effective and fast way to
characterize mudrocks that can be widely applied in industrial
exploration. Here, we demonstrate a novel integrated protocol
for chemofacies characterization of organic-rich mudrocks based
on energy-dispersive x-ray fluorescence (ED-XRF) elemental
composition measurements, principal components analysis
(PCA), and k-means clustering. Using PCA and k-means cluster-
ing of 5000 ED-XRF measurements from three cores, three
chemofacies were identified from the Upper Pennsylvanian
organic-rich Cline Shale in the Midland Basin, Texas. Each che-
mofacies is characterized by a unique major and trace element
composition and can be correlated to specific depositional envi-
ronments (e.g., sediment provenance, detrital input, redox condi-
tions, and primary productivity) with certain sedimentary struc-
tures and primary grain assemblage composition. In addition,
 each chemofacies characterized by a certain primary
grain assemblage composition will follow predictable
sedimentological and diagenetic pathways that have
significant implications for the evolution of bulk rock
petrophysical and mechanic properties. This study
demonstrates a data analytical approach and protocol
for mudrock chemofacies characterization. Further-
more, this approach can be applied to a wide range of
geochemical studies that go beyond unconventional
resource assessment to include any study that
requires large multivariate data sets.
BACKGROUND
Paleogeography and Depositional
Environment of the Cline Shale
During the Late Pennsylvanian, the Midland Basin
was an epicratonic foreland basin in front of the Oua-
chita orogenic belt (Figure 1) (Yang and Dorobek,
1995). The connection of the Midland Basin to the
Panthalassa ocean (Figure 1) was restricted by
the serpentine-shaped Great Permian seaway
(1000 km length), which included several deep
basins and interconnecting shallow-water sills (Figure
1) (Algeo and Heckel, 2008). Thus, the hydrographic
circulation in the Midland Basin was severely
restricted, especially during the sea-level lowstand
(Peng et al., 2021).
The rapid subsidence of the Midland Basin dur-
ing the Late Pennsylvanian caused the deposition
of the basinal organic-rich Cline Shale (TOC:
0.13–9.9 wt. %, mean: 2.64 wt. %; Peng et al., 2021)
and mixed siliciclastic-carbonate shelf deposits (Fig-
ure 2A) (Brown et al.,1990). The Ouachita orogenic
belt to the east of the Eastern shelf is interpreted to
have been the dominant siliciclastic provenance for
the Cline Shale (Brown et al.,1990). Furthermore,
previous stratigraphic studies suggest that the high
frequency and high amplitude glacioeustatic sea-level
variation during the Late Pennsylvanian controlled
the lithofacies cyclicity revealed in the Cline Shale
(Peng, 2021; Peng et al., 2021). Specifically, silici-
clastic depositional systems transported sediment
westward across the entire Eastern shelf (Figure 2)
from the Ouachita orogenic belt and were responsi-
ble for large amounts of detrital materials deposited
in the basin, forming siliciclastic intervals during
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sea-level lowstand (Brown et al.,1990; Hentz et al.,
2017; Peng, 2021; Peng et al., 2021). In contrast, car-
bonate platforms developed on the Eastern shelf and
deep Midland Basin during sea-level highstand
(Brown et al.,1990; Hentz et al., 2017; Peng, 2021;
Peng et al., 2021).
Problems in Unconventional Resources
Exploration
For decades, the Upper Pennsylvanian organic-rich
Cline Shale was just considered as a source rock for
hydrocarbon accumulation in the Midland Basin
(Hamlin and Baumgardner, 2012). Producible shale
oil was recently discovered in the Cline Shale, and
good unconventional reservoir properties were
observed (Hamlin and Baumgardner, 2012). How-
ever, the high degree of heterogeneity of this marine
mudrock succession increases the difficulty of shale
oil production (Jacobs, 2013). Specifically, ductile
layers with high clay-mineral content are unfavorable
for hydraulic fracturing. In addition, layers with low
TOC are unfavorable for commercial hydrocarbon in
situ accumulation.
DATA AND METHODS
Three cores discussed in this study are from the
Stroman Ranch 5H well, Sterling County, Texas
(length: 68 m; surface location: 31.9018500 N,
101.0751722 W), Adoue 1H well, Mitchell
County, Texas (length: 88 m; surface location:
32.3093722 N, 100.8947698 W), and Horwood
2151H well, Sterling County, Texas (length: 83 m;
location: 31.9051667 N, 100.9396750 W), respec-
tively (Figure 2). All three cores include the entire
Cline Shale succession. The detailed workflows
for ED-XRF elemental analyses, rock mechanical
property analyses, and petrographic observation are
described below.
Bulk Geochemical Analyses
The ED-XRF measurements for core samples from
wells Adoue 1H (1607 measurements; each mea-
surement contains 25 major and trace elements) and
Stroman Ranch 5H (1482 measurements; each mea-
surement contains 25 major and trace elements) was
PENG AND LARSON 439
 Figure 1. Regional paleogeography of the Great Permian seaway (GPS) and Late Pennsylvanian Midcontinent sea (LPMS). The map is
after Peng et al. (2021), which is modified from Blakey (2007) and Algeo et al. (2008). AnB 5 Anadarko Basin; ARM 5 Ancestral Rocky
Mountains, MB 5 Midland Basin.

conducted at 4-cm spacing to obtain high- Horwood 2151H were compiled from Peng et al.
resolution elemental logs. The ED-XRF analyses (2021) (Table S1, supplementary material as AAPG
were conducted using a Bruker Elemental TRACER Datashare 145 at www.aapg.org/datashare). The
IV-SD ED-XRF analyzer at the Bureau of Economic TOC measurements were conducted following the
Geology, The University of Texas at Austin. The modified direct combustion method (Peters and
XRF spectra for major elements were generated Cassa, 1994) using the LECO CS-200 analyzer.
under helium using an Rh tube set at 15 kV and
34.4 mA with 15 s counted time. The XRF spectra Analysis of Rock Mechanical Properties,
for trace elements were analyzed under helium at 40 Porosity, and Permeability
kV and 25 mA (45 s counted time) with an aluminum
(Al)-titanium (Ti)-copper (Cu) filter to attenuate Unconfined compressive strength (UCS) is used as a
characteristic major-element x-rays. All of the raw proxy for rock brittleness in this study (Zahm and
ED-XRF data were then calibrated using proprietary Enderlin, 2010). The microrebound hammer
Bruker calibration software (S1CalProcess; Rowe (MRH)-derived UCS was conducted on the Hor-
et al., 2012). The average unknown standard devia- wood 2151H core for 4-cm spacing (exactly the
tions for different elements obtained from the samples with ED-XRF analyses) (Table S1, supple-
ED-XRF analyses are given in Table 1 (Rowe et al., mentary material as AAPG Datashare 145 at www.
2012). The 4-cm (2-in.) spacing ED-XRF data aapg.org/datashare) using the Equotip Bambino (an
sets of Horwood 2151H well (1649 ED-XRF meas- MRH; Proceq SA, Schwerzenbach, Switzerland) in
urements; each measurement contains 25 major and this study. To avoid the “volume effect” (i.e., smaller
trace elements) are compiled from Peng et al. sample volumes yield significant underestimation of
(2021). the UCS), measurements were only conducted on
A total of 298 bulk TOC measurements were samples with a volume larger than 200 cm3 as sug-
compiled from published literature. Specifically, 115 gested by Brooks et al. (2016). In general, samples
TOC data sets from wells Adoue 1H (43 samples) with a volume less than 200 cm3 are limited and do
and Stroman Ranch 5H (72 samples) were compiled not bias any specific chemofacies. The detailed
from Zheng (2016) (Table S1, supplementary mate- workflow for this measurement follows Zahm and
rial as AAPG Datashare 145 at www.aapg.org/ Enderlin (2010). For each sample (volume >200
datashare). Moreover, 183 TOC data sets from well cm3), 10 measurements were conducted at different

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 Figure 2. (A) Map of the Midland Basin showing the distribution of the Cline Shale, regional tectonic unit, and location of studied cores.
The map is after Peng et al. (2020b), which is modified from Wright (2011) and Baumgardner et al. (2016). (B) Upper
Pennsylvanian–lower Permian stratigraphy of the Midland Basin. The map is after Peng et al. (2021), which is modified from Baumgardner
et al. (2016). CBP 5 Central Basin platform; DB 5 Delaware Basin; ES 5 Eastern shelf; HA 5 Horseshoe atoll; MA 5 Matador arch;
MB 5 Midland Basin; NA 5 North America; NM 5 New Mexico; NWS 5 Northwest shelf; OA 5 Ozona arch; SC 5 Sheffield channel;
TEX 5 Texas.

locations along the horizontal bedding. Then, the Petrographic Observation

average value (the highest and lowest value were
removed before calculation) was regarded as the final
MRH-derived UCS value for the sample and
reported as Leeb hardness (HLD; Leeb, 1979).
Fifty-nine Gas Research Institute (GRI) crushed-
rock porosity and permeability data sets from well
Horwood 2151H were compiled from Zheng (2016)
(Table S1, supplementary material as AAPG Data-
share 145 at www.aapg.org/datashare). The GRI
porosity and permeability were measured via Boyles
Law helium porosimetry on crushed material with
as-received liquids in place (Luffel et al.,1996).
A total of 265 thin sections (0.9 m spacing on aver-
age) obtained from three cores that captured all
lithofacies were used for conventional transmitted
polarized light microscopy observation. Among
them, a total of 32 representative samples were
selected for field-emission scanning electron micro-
scope (SEM) observation (FEI Nova NanoSEM
430, Thermo Fisher Scientific, Waltham, MA). The
secondary electron imaging, backscattered electron
imaging, x-ray elemental mapping by energy-
dispersive spectroscopy (twin Bruker 30 mm2

PENG AND LARSON 441

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 Table 1. The Average Unknown Standard Deviations for 2005; Schoepfer et al., 2015). In addition, rare detri-
Elements Obtained from Energy-Dispersive X-Ray Fluorescence tal grains enriched in these two elements (e.g., detri-
Elemental Analyses (Rowe et al., 2012) tal apatite and barite) were identified from the Cline
Shale, and thus, elements Ba and P were used as
Average Unknown Standard
Elements Deviations (Weight Concentration) proxies for primary productivity.
Elements zirconium (Zr), Ti, rubidium (Rb), and
Al, % 0.1 thorium (Th) are enriched in detrital heavy minerals
Si, % 0.2 (e.g., zircon) and generally immobile during the post-
Ca, % 0.01
depositional diagenetic process (Sageman and Lyons,
Mg, % 0.2
2004). Thus, Zr, Ti, Rb, and Th can be good proxies
K, % 0.02
S, % 0.1 for detrital input (Caplan and Bustin, 1999; Doveton
Mn, % 0.002 and Merriam, 2004; Ver Straeten et al., 2011).
Fe, % 0.01 Nine redox-sensitive trace elements (RSTEs;
Ti, % 0.02 cobalt [Co], chromium [Cr], Cu, molybdenum
Zr, ppm 4 [Mo], nickel [Ni], lead [Pb], uranium [U], vanadium
Ba, ppm 147 [V], and zinc [Zn]) and element sulfur (S) exhibit
P, % 0.01
strong enrichment under reducing conditions and
Cu, ppm 14
Ni, ppm 8
considered as redox proxies in this study (Tribovil-
U, ppm 3 lard et al., 2006; Algeo and Liu, 2020). Algeo and
V, ppm 44 Liu (2020) suggest that these nine RSTEs are shown
Zn, ppm 11 to be generally more reliable and superior to other
Cr, ppm 9 redox proxies such as bimetal ratios and the C-S-Fe
Mo, ppm 1 system on the basis of reassessment of redox proxies
Th, ppm 1 from 55 Phanerozoic marine units.
Rb, ppm 3
The other three elements acquired from the
Sr, ppm 1
ED-XRF measurements (strontium, manganese, and
iron) display very mobile behavior in both oxic and
detectors; Bruker Corporation, Billerica, Massachu- anoxic environments (Tribovillard et al., 2006; Wei
setts), and cathodoluminescence (CL) imaging and Algeo, 2020). Thus, these three elements will
(Gatan ChromaCL detector; Gatan, Pleasanton, Cal- not be used as any specific environmental proxies in
ifornia) were integrated during SEM observation. this study.

PCA and k-Means Clustering

Proxies for Chemofacies Characterization
A total of 25 bulk elements can be obtained from the
ED-XRF analyses in this study. These 25 elements
can be divided into 5 categories.
Six major elements (Al, silicon [Si], calcium
[Ca], sodium [Na], potassium [K], and magnesium
[Mg]) compose bulk mineral composition of
mudrocks (Baumgardner et al., 2016). Specifically,
we used Al to approximate clay minerals, Si to
approximate quartz, Ca to approximate calcite, Na
to approximate albite, K to approximate K-feldspar,
and Mg to approximate dolomite.
Elements barium (Ba) and phosphorus (P) are
essential nutrients for marine phytoplankton growth
(Bishop, 1988; Dymond et al., 1992; Schenau et al.,
Principal components analysis and k-means clustering
are widely used in geological classification (e.g.,
Handwerger et al., 2015; Amin et al., 2021). The
ED-XRF geochemical data sets were processed using
the methods outlined in Larson et al. (2019). Briefly,
PCA is used to compress the multivariate ED-XRF
data sets down to a smaller number of
components (i.e., principal components) that are
required to describe the variance and covariance of
the major and trace elements. This approach makes
it much easier to focus on the primary variations of
the total 25 elements from ED-XRF analysis (Larson
et al., 2019). Prior to conducting PCA, the data sets
are queried for analytical outliers; samples that have
concentrations that are greater than four standard

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 deviations from the mean for each element are iden-
tified as outliers and excluded from PCA.
The PCA of the 25 major and trace elements
derived from ED-XRF is conducted by proprietary
software Matlab (Matrix Laboratory version 2018b;
MathWorks, United States), in which each element
was treated as a variable. The principal component
algorithm is a singular value decomposition (Jolliffe,
2002). The robustness of PCA results was further
tested on the basis of two standard procedures, Kaiser-
Meyer-Olkin statistic (Cureton and D’Agostino,
1983) and Bartlett sphericity test (Grossman et al.,
1991), before reporting. We extracted up to 25 princi-
pal components (Table S2, supplementary material as
AAPG Datashare 145 at www.aapg.org/datashare).
The k-means clustering (Lloyd, 1982) was con-
ducted on the basis of the variances of the principal
components of each mudrock sample reported from
PCA. The k-means clustering was also performed on
proprietary software Matlab (Matrix Laboratory ver-
sion 2018b; MathWorks, United States). In each
cluster, k-means clustering calculates and minimizes
the sum of the distances between the centroid and all
samples of the cluster. The squared Euclidean dis-
tance metric is used to determine distances. The
most significant advantage of using k-means cluster-
ing is that we can manually assign and adjust the
number of final clusters (k) based on geological back-
ground and compare clustering solutions for different
values of k to determine an optimal number of clus-
ters for the data sets.
Figure 3. The variance fractions of each principal component (PC). A total of 25 PCs were extracted. The variance explained by a specific
PC is the ratio between the variance of that PC and the variance of the total database.
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RESULTS
General Bulk Geochemical and
PCA Results
The results of the PCA of 5000 ED-XRF measure-
ments are summarized in Table S2 (supplementary
material as AAPG Datashare 145 at www.aapg.org/
datashare). The first principal component (PC 1)
accounted for a much higher fraction of total data-
base variance (27.8%) than higher-order components
(Figure 3). The second (PC 2) to fifth principal com-
ponents (PC 5) accounted for 14.4%, 11.4%, 8.1%,
and 5.4% of the total variance, respectively (Figure
3). The first five principal components accounted for
70% of the total variance (Figure 3). In contrast,
higher-order principal components accounted for
very small amounts of the total variance (each less
than 5%; Figure 3) and yielded very low factor load-
ings (Table S2, supplementary material as AAPG
Datashare 145 at www.aapg.org/datashare).
Figure 4 is the crossplot of PC 1 and PC 2 with
projections of 25 measured elements. The projec-
tions of siliciclastic residing elements (i.e., Al, Si, Na,
and K) are adjacent to the detrital input proxies (Th,
Rb, Ti, and Zr), and all of these elements project
toward the negative direction of the PC 1 axis (Figure
4). In contrast, the projections of carbonate residing
elements (i.e., Ca and Mg) exhibit a reverse pattern
and project toward the positive direction of the PC 1
axis (Figure 4). The projections of nine RSTEs and S
PENG AND LARSON 443
 Figure 4. Crossplot of the first two principal components (PC 1 and PC 2) of the energy-dispersive x-ray fluorescence–derived 25
elements of the Cline Shale. The PC 1 generally represents the partition of mineral-composition–sensitive elements and detrital input prox-
ies; the positive direction is more Ca and Mg-rich, whereas the negative direction has more detrital input proxies and is Al, Si, K, Na-rich.
The PC 2 generally represents the enrichment of redox-sensitive elements; the positive direction is redox-sensitive elements-rich, whereas
the negative direction is redox-sensitive elements-depleted. The k-means clustering analysis reveals three clusters that represent three dif-
ferent chemofacies: oxic-suboxic detrital-enriched argillaceous mudrocks, anoxic siliceous mudrocks, and oxic-suboxic intrabasinal carbo-
nates. Elements highlighted by five different colors indicate five categories of proxies as defined in the legend, respectively. Two elements
with more adjacent projections in the crossplot suggest that they are more correlatable.

are toward the positive direction of the PC 2 axis
(Figure 4).
In summary, PC 1 generally represents the parti-
tion of mineral-composition-sensitive elements: high
PC 1 suggests Ca and Mg rich, whereas low PC 1 sug-
gests Al, Si, K, Na, Th, Rb, Ti, and Zr rich. The PC 2
generally represents the enrichment of RSTEs: high
PC 2 suggests RSTE rich, whereas low PC 2 suggests
RSTE depleted.
PCA-Based Chemofacies Classification
Three chemofacies clusters were chosen in this study
because of the following reasons (Figure 4): (1) we
show that three clusters are necessary to capture the
spread of the ED-XRF data sets of the Cline Shale
after reiterations testing, and (2) geologic considera-
tions (i.e., redox conditions, sediment provenance,
and bulk mineral compositions) provide the additional
justification for the number of clusters ultimately cho-
sen, besides pure mathematical reasoning.
The nomenclature of each chemofacies in this
study is based on the enrichment of RSTEs (i.e.,
redox conditions: oxic, suboxic, or anoxic), detrital
input proxies (i.e., sediment provenance: detrital-
enriched or intrabasinal), and mineral-composition-
sensitive elements (i.e., mineral composition:
argillaceous, siliceous, or carbonate). Based on these
criteria, three chemofacies were named oxic-suboxic
detrital-enriched argillaceous mudrocks, anoxic
siliceous mudrocks, and oxic-suboxic intrabasinal car-
bonates, respectively (Figure 4). The content of
representative elements and reservoir properties of
different chemofacies is summarized in Table 2.
Oxic-Suboxic Detrital-Enriched Argillaceous
Mudrocks
The oxic-suboxic detrital-enriched argillaceous mud-
rocks are characterized by the highest Al content,
intermediate to high Si content, and low Ca and Mg
content (Figure 5; Table 2). The concentration of Al,
Si, Ca, and Mg in oxic-suboxic detrital-enriched

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 Table 2. Variations of Representative Element Concentrations and Bulk Rock Properties of Different Chemofacies in the
Cline Shale

Chemofacies
Elements and Reservoir Oxic-Suboxic Detrital-Enriched Oxic-Suboxic Intrabasinal
Properties Argillaceous Mudrocks Anoxic Siliceous Mudrocks Carbonates

Al, wt. % 3.97–9.54 (6.68; 6.78) 2.64–8.75 (5.87; 5.74) 0–4.29 (1.13; 1.46)
Si, wt. % 15.08–34.39 (24.78; 24.62) 17.98–36.50 (27.17; 26.93) 0–25.75 (7.07; 8.95)
Ca, wt. % 0.02–7.75 (1.97; 2.64) 0.03–3.19 (1.13; 1.47) 2.51–37.59 (22.44; 21.89)
Mg, wt. % 0–3.70 (0.96; 0.72) 0–1.79 (0.88; 0.67) 0.09–10.25 (2.46; 3.24)
Ti, wt. % 0.24–0.48 (0.36; 0.36) 0.20–0.43 (0.32; 0.31) 0–0.25 (0.07; 0.09)
Zr, ppm 83.40–187.44 (132.34; 142.81) 37.64–165 (119; 118) 0–93 (26; 34)
Ni, ppm 0–85 (38.52; 39.63) 34–125 (75.84; 79.97) 0–41.02 (17; 19.35)
Cu, ppm 0–57.65 (26; 25.82) 17–93.3 (52; 55.47) 0–31.91 (0; 6.63)
Mo, ppm 0–14 (6; 5.94) 0–21.62 (10; 11) 0–5.78 (0; 1.31)
TOC, wt. % 0.13–3.62 (1.4; 1.52) 0.67–9.88 (5.07; 5.26) 0.19–1.13 (0.70; 0.83)
Porosity, vol. % 0.52–1.90 (1.22; 1.28) 0.46–3.29 (2.04; 2.08) 0.37–1.69 (0.70; 0.86)
4
Permeability, 10 md 0.38–1.01 (0.76; 0.77) 0.57–2.9 (1.53; 1.53) 0.44–0.78 (0.69; 0.69)
UCS, HLD 322–585 (494; 478) 529–675 (586; 591) 636–866 (776; 759)
The first and second value in parentheses suggest the median value and mean value, respectively.
Abbreviations: HLD = Leeb hardness; TOC = total organic carbon; UCS = unconfined compression strength.

argillaceous mudrocks ranges from 3.9% to 9.54% Oxic-Suboxic Intrabasinal Carbonates

(median: 6.68%), 15.08% to 34.39% (median:
24.78%), 0.02% to 7.75% (median: 1.97%), and 0%
to 3.7% (median: 0.96%), respectively (Figure 5;
Table 2). Contents of detrital proxies (e.g., Ti and Zr)
are highest in the oxic-suboxic detrital-enriched argil-
laceous mudrocks (Figure 6; Table 2). In contrast,
contents of redox proxies (e.g., Ni, Cu, and Mo) are
moderate to low in the oxic-suboxic detrital-enriched
argillaceous mudrocks (Figure 7; Table 2).
Anoxic Siliceous Mudrocks
The anoxic siliceous mudrocks are characterized by
the highest Si content in the data set, intermediate
Al content, and low Ca and Mg content (Figure 5;
Table 2). The concentration of Al, Si, Ca, and Mg in
anoxic siliceous mudrocks ranges from 2.64% to
8.75% (median: 5.87%), 17.98%–36.50% (median:
27.17%), 0.03%–3.19% (median: 1.13%), and
0%–1.79% (median: 0.88%), respectively (Figure 5;
Table 2). The concentration of detrital proxies (e.g.,
Ti and Zr) in the anoxic siliceous mudrocks are inter-
mediate and lower than that of oxic-suboxic detrital-
enriched argillaceous mudrocks (Figure 6; Table 2).
Furthermore, the concentration of redox proxies
(e.g., Ni, Cu, and Mo) are highest in the anoxic sili-
ceous mudrocks (Figure 7).
The oxic-suboxic intrabasinal carbonates are charac-
terized by the highest Ca and Mg content, low Al
content, and low Si content (Figure 5; Table 2). The
concentration of Al, Si, Ca, and Mg in oxic-suboxic
intrabasinal carbonates ranges from 0% to 4.29%
(median: 1.13%), 0% to 25.75% (median: 7.07%),
2.51% to 37.59% (median: 22.44%), and 0.09% to
10.25% (median: 2.46%), respectively (Figure 5;
Table 2). Content of both detrital proxies (e.g., Ti
and Zr) and redox proxies (e.g., Ni, Cu, and Mo) are
lowest in the oxic-suboxic intrabasinal carbonates
(Figures 6, 7).
Petrographic Characteristics
Oxic-Suboxic Detrital-Enriched Argillaceous
Mudrocks
The oxic-suboxic detrital-enriched argillaceous
mudrocks are generally structureless to faint lami-
nated at microfacies (thin-section) level of observa-
tion (Figure 8A, B). In most cases, the primary grain
assemblages in the oxic-suboxic detrital-enriched
argillaceous mudrocks are predominantly composed
of detrital clay minerals (Figure 8B, C). Besides detri-
tal clay minerals, silt-sized quartz, detrital carbonate
grains, carbonate allochems (commonly extra-large,

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 Figure 5. Box-and-whisker plots of energy-dispersive x-ray fluorescence (A) Al, (B) Si, (C) Ca, and (D) Mg content for each chemofacies
of the Cline Shale. The “box” depicts the 25th and 75th percentiles of element concentration, the “whiskers” depict the minimum and max-
imum element concentration, and the central line indicates the median value. The outliers are plotted individually using the red cross sym-
bol. Data sets will be classified as outliers if they are greater than q3 1 w 3 (q3 – q1) or less than q1 – w 3 (q3 – q1), where w is the
maximum whisker length, and q1 and q3 are the 25th and 75th percentiles of the sample data, respectively. n 5 number of samples.

millimeter-scale robust molluscan skeletal frag- observed in the oxic-suboxic detrital-enriched argilla-
ments), mica, heavy minerals, and feldspar can be ceous mudrocks (Figure 8F).
also observed chaotically “floating” in the clay matrix
(Figure 8D, E). In general, rare intrabasinal grain Anoxic Siliceous Mudrocks
assemblages were observed in oxic-suboxic detrital- The anoxic siliceous mudrocks have well-defined
enriched argillaceous mudrocks (Figure 8B–D). planar to wavy lamination (Figure 9A, B). This litho-
Furthermore, bioturbations and burrows can be facies is composed of thin (commonly <10 mm)

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 Figure 6. Box-and-whisker plots of energy-dispersive x-ray fluorescence (A) Ti and (B) Zr content for each chemofacies. The “box”
depicts the 25th and 75th percentiles of element concentration, the “whiskers” depict the minimum and maximum element concentration,
and the central line indicates the median value. The outliers are plotted individually using the red cross symbol. Data sets will be classified
as outliers if they are greater than q3 1 w 3 (q3 – q1) or less than q1 – w 3 (q3 – q1), where w is the maximum whisker length, and q1
and q3 are the 25th and 75th percentiles of the sample data, respectively. n 5 number of samples.

normally graded beds with erosive basal division
comprised of detrital silt quartz and rip-up clasts
(Figure 9C) and homogenized top division composed
of organomineralic aggregates (OMAs; Macquaker
et al., 2010) (Figure 9D, E). Furthermore, in some
specific samples, a high concentration of biosiliceous
allochems, such as sponge spicules and radiolarians
(Figure 9F–H), can be identified. These biosiliceous
allochems are generally showing pale-mauve to dark
grayish CL color and low CL intensity (red arrow in
Figure 9H) compared to extrabasinal detrital quartz,
which is characterized by brighter reddish CL color
(yellow arrows in Figure 9H). In addition, the projec-
tion of Si in Figure 4 is slightly deviated from projec-
tions of detrital proxies, such as Ti and Zr, reflecting
the presence of authigenic quartz in some samples.
However, the detrital silt-sized quartz is still the
dominant form of quartz in anoxic siliceous
mudrocks from petrographic observation. These bio-
siliceous allochems may only occur in very high
abundance in limited samples. This observation is
consistent with previous research that detrital quartz
is the dominant form of quartz in the Cline Shale
based on SEM-based CL observation and quantita-
tive point count (Peng et al., 2020a). In addition, no
burrows were observed from any samples of anoxic
siliceous mudrocks in this study.
Oxic-Suboxic Intrabasinal Carbonates
The oxic-suboxic intrabasinal carbonates are generally
massive and experienced early dolomitization
(Figure 10A, B). Most primary grains were replaced
by the euhedral rhombohedral dolomite, which
commonly obscures the primary grain assemblages
in this chemofacies (Figure 10B). In addition,
the matrix of oxic-suboxic intrabasinal carbonates is
widely cemented by the euhedral rhomb dolomite
(Figure 10C, D). In some samples without heavy dia-
genetic overprinting, two major categories of primary
grain assemblages can be observed: pelagic allo-
chems, such as calcispheres (Figure 10B), conodonts
(Figure 10F), peloids, and radiolarians (calcified;
Figure 10G, H); and benthic carbonate allochems
from the shallow-water platform (Figure 10E), such
as fusulinids, echinoids, crinoids, and robust mollusk
skeletal fragments.

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 Figure 7. Box-and-whisker plots of energy-dispersive x-ray fluorescence (A) Ni, (B) Cu, and (C) Mo content for each chemofacies. The
“box” depicts the 25th and 75th percentiles of element concentration, the “whiskers” depict the minimum and maximum element concen-
tration, and the central line indicates the median value. The outliers are plotted individually using the red cross symbol. Data sets will be
classified as outliers if they are greater than q3 1 w 3 (q3 – q1) or less than q1 – w 3 (q3 – q1), where w is the maximum whisker length,
and q1 and q3 are the 25th and 75th percentiles of the sample data, respectively. n 5 number of samples.

Bulk TOC, Petrophysical, and Rock UCS (Figure 11; Table 2). The TOC, UCS, poros-
Mechanical Properties ity, and permeability of oxic-suboxic detrital-
enriched argillaceous mudrocks range from 0.13
Oxic-Suboxic Detrital-Enriched Argillaceous wt. % to 3.62 wt. % (median: 1.4 wt. %), 322
Mudrocks HLD to 585 HLD (median: 494 HLD), 0.52% to
The bulk TOC, petrophysical (porosity and perme- 1.90% (median: 1.22%), and 3.8 · 10 5 md to
ability), and rock mechanical properties (reported as 1.01 · 10 4 md (median: 7.6 · 10 5 md), respec-
UCS) of the Cline Shale exhibit significant variations tively (Figure 11; Table 2).
among different chemofacies (Figure 11; Table 2).
Specifically, the oxic-suboxic detrital-enriched argil- Anoxic Siliceous Mudrocks
laceous mudrocks are characterized by low TOC, The anoxic siliceous mudrocks are characterized
low porosity, low permeability, and the lowest by the highest TOC, the highest porosity, the highest

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 Figure 8. Representative photographs of oxic-suboxic detrital-enriched argillaceous mudrocks. (A) Core photograph of oxic-suboxic detri-
tal-enriched argillaceous mudrocks showing homogeneous and structureless texture, Adoue 1H, 2256.6 m. (B) Homogeneous and struc-
tureless texture in the thin section. In general, rare silt- or sand-size detrital siliciclastic particles (e.g., quartz and feldspar) are observed. (C)
Enlarged area of box in (B) suggests the matrix of oxic-suboxic detrital-enriched argillaceous mudrocks are almost exclusively composed of
detrital clay minerals. (D) An energy-dispersive spectroscopy map showing that limited silt-sized grains (less than 10%) are mainly com-
posed of detrital quartz (red) with minor amounts of albite (aqua) and calcite (blue) after Peng et al. (2020a). Silt-size grains (less than
10%) appear to “float” in the clay matrix (green) without a touching framework. Horwood 2151H, 2478.8 m. (E) Outsized robust molluscan
skeletal fragments (arrows) were observed to “float” in the clay matrix. Adoue 1H, 2215.7 m. (F) Millimeter-scale burrows (arrows) can be
observed in oxic-suboxic detrital-enriched argillaceous mudrocks. Horwood 2151H, 2967.1 m. BSE 5 backscattered electron.

permeability, and moderate to high UCS (Figure 11; 10 4 md (median: 1.53· 10 4

md), respectively
Table 2). The TOC, UCS, porosity, and permeability (Figure 11; Table 2).
of anoxic siliceous mudrocks range from 0.67 wt. %
to 9.88 wt. % (median: 5.07 wt. %), 529 HLD to Oxic-Suboxic Intrabasinal Carbonates
675 HLD (median: 586 HLD), 0.46% to 3.29% The oxic-suboxic intrabasinal carbonates are character-
(median: 2.04%), and 5.7 · 10 5 md to 2.9 · ized by the lowest TOC, the lowest porosity, the lowest

PENG AND LARSON 449

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 Figure 9. Representative photographs of anoxic siliceous mudrocks. (A) Core photograph of anoxic siliceous mudrocks showing wavy to
planar laminations. Adoue 1H, 2422.1 m. (B) Thin normally graded beds (separated by the yellow dashed line and red arrows aside) with
basal silt-sized particle-rich division and top organic-rich homogenized division. The basal silt-sized particle-rich division is commonly char-
acterized by a sharp and erosional base (yellow arrow). Horwood 2151H, 2457.3 m. (C) Basal silt-sized particle-rich divisions are mainly
composed of detrital silt-sized quartz (yellow arrows) and rip-up clasts (red arrows). Adoue 1H, 2242.1 m. (D) Enlarged area of box in (B)
suggests top organic-rich homogenized division is mainly composed of detrital clay matrix and organomineralic aggregates (OMA; arrows).
(E) Backscattered electron (BSE) images of OMA. Horwood 2151H, 2457.3 m. (F) Energy-dispersive spectroscopy map of sponge spicules
(arrow). Horwood 2151H, 2457.5 m. (G) Energy-dispersive spectroscopy map of radiolarian (red arrow) and silt-sized extrabasinal detrital
quartz (yellow arrows). Horwood 2151H, 2460.3 m. (H) Cathodoluminescence (CL) image of the dashed-line area in (G). Radiolarian (red
arrow) shows pale-mauve to dark grayish CL color and low intensity compared to extrabasinal detrital quartz (yellow arrows) characterized
by reddish CL color in the rock matrix. Horwood 2151H, 2460.3 m. (B) Image was created after Peng et al. (2021), and images (C) and (E)
were created after Peng (2021).

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 Figure 10. Representative photographs of oxic-suboxic intrabasinal carbonates. (A) Core photograph of oxic-suboxic intrabasinal carbo-
nates showing massive texture. Adoue 1H, 2217.1 m. (B) Enlarged area of box in (A) suggests oxic-suboxic intrabasinal carbonates have
experienced early dolomitization. Primary grain assemblages (possibly calcispheres; arrows) are difficult to accurately identify.
(C) Enlarged area of box in (B) suggests the matrix of oxic-suboxic intrabasinal carbonates are cemented by euhedral rhombus dolomite
crystal, the thin section was stained in red using Alizarin Red S. (D) Energy-dispersive spectroscopy map of oxic-suboxic intrabasinal carbo-
nates showing widely distribution of euhedral rhombus dolomite cementation throughout the rock matrix. Horwood 2151H, 2415.1 m. (E)
Fusulinid (yellow arrow) and echinoids (red arrows) from the shallow-water platform can be observed in some samples without heavy
diagenetic overprinting. Horwood 2151H, 2409.8 m (F) Backscattered electron (BSE) images of conodont (arrow). Stroman Ranch 5H,
2494.0 m. (G) Radiolarians (arrows) can be identified in limited samples without significant dolomitization. Stroman Ranch 5H, 2494.0 m.
(H) BSE images of radiolarian (arrow), created after Peng et al. (2020b). Horwood 2151H, 2457.5 m. BSE.

PENG AND LARSON 451

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 Figure 11. Box-and-whisker plots of (A) total organic carbon (TOC), (B) porosity, (C) permeability, and (D) unconfined compressive
strength (UCS) of each chemofacies. The “box” depicts the 25th and 75th percentiles of element concentration, the “whiskers” depict the
minimum and maximum element concentration, and the central line indicates the median value. The outliers are plotted individually using
the red cross symbol. Data sets will be classified as outliers if they are greater than q3 1 w 3 (q3 – q1) or less than q1 – w 3 (q3 – q1),
where w is the maximum whisker length, and q1 and q3 are the 25th and 75th percentiles of the sample data, respectively. HLD 5 Leeb
hardness; n 5 number of samples.

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 permeability, and the highest UCS (Figure 11; Table 2).
The TOC, UCS, porosity, and permeability of oxic-
suboxic intrabasinal carbonates range from 0.19 wt. %
to 1.13 wt. % (median: 0.7 wt. %), 636 HLD to 866
HLD (median: 776 HLD), 0.37% to 1.69% (median:
0.7%), and 4.4 · 10 5 md to 7.8 · 10 5 md (median:
6.9 · 10 5 md), respectively (Figure 11; Table 2).
DISCUSSION
Relationships between Element
Composition, Grain Assemblages, and
Depositional Environments
Oxic-Suboxic Detrital-Enriched Argillaceous
Mudrocks
The oxic-suboxic detrital-enriched argillaceous
mudrocks are enriched in Al, K, Si, Na, Th, Zr, Rb,
and Ti and depleted in RSTEs (Table 2). The high
concentration of Al, K, Si, and Na are interpreted to
be caused by the high volume of detrital clay miner-
als, as also observed in thin sections (Figure 8).
Furthermore, the relatively high concentration of Th,
Zr, Rb, and Ti also indicates the detrital siliciclastic
origin of clayey rock components. The relatively low
concentrations of RSTEs indicate an overall suboxic
redox benthic condition, which is consistent with
burrows encountered in thin sections (Figure 8F) and
textures of pyrite framboids (Peng et al., 2021). The
oxic-suboxic detrital-enriched argillaceous mudrocks
are also characterized by moderate to low Ca and Mg
concentrations. Based on petrographic observation,
Mg and Ca in the oxic-suboxic detrital-enriched
argillaceous mudrocks are most likely associated with
some specific feldspar, mica, detrital carbonate
grains, and mollusk skeletal fragments (Figure 8D,
E). These robust mollusk skeletal fragments (Figure
8E) have been interpreted as debrites derived from
shallow-water shelf (Peng, 2021).
Based on the stratigraphic framework of the
Cline Shale established by Peng et al. (2021) and
Peng (2021), the oxic-suboxic argillaceous mudrocks
were interpreted as transgressive deposits. These
detrital clay minerals are believed to be derived from
siliciclastic transportation systems (e.g., fluvial hyper-
pycnal input) developed on the Eastern shelf during
this period (Figure 2) (Peng, 2021).
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Anoxic Siliceous Mudrocks
The anoxic siliceous mudrocks are enriched in RSTEs
and Si compared to the other two chemofacies
(Figures 5, 7). The highest concentration of Si in
anoxic siliceous mudrocks may attribute to two popu-
lations of grain assemblages in the basal silt-sized parti-
cle-rich division (Figure 9C): (1) silt-sized detrital
quartz and (2) biosiliceous allochems. The silt-sized
detrital quartz is the dominant form of quartz in the
anoxic siliceous mudrocks (as well as the entire Cline
Shale) based on petrographic observation. This petro-
graphic evidence is further supported by the moderate
to high Ti and Zr content in anoxic siliceous mudrocks
(Figure 6), suggesting considerable detrital input. This
discovery suggests that the predominant quartz types
in the Cline Shale are different from some other oil-
producing anoxic marine shales in the United States,
such as the Mississippian Barnett Shale, Fort Worth
Basin (Milliken et al., 2012), and the Cretaceous
Mowry Shale, Rocky Mountains (Milliken and Olson,
2017), where higher concentrations of biosiliceous
allochems (mainly sponge spicules and radiolarians)
were observed. The erosive silt-sized particle-rich
basal division (Figure 9C) was interpreted as distal tur-
bidite during sea-level lowstand by Peng (2021) based
on the high concentration of silt-sized detrital quartz,
rip-up clasts, erosional base, planar laminations, and
considerable content of detrital proxies. The Ouachita
orogenic belt (Figure 1) to the east of the Eastern shelf
was an important source of clastic material to the
basin, and these eroded clastics were redeposited
increasingly westward, forming distal turbidite in the
basin during sea-level lowstand (Brown et al., 1990;
Peng, 2021). However, between each episodic sub-
aqueous turbidity current, there was sufficient time
for the pelagic deposition of the organic-rich homoge-
nized top division as shown in Figure 9D (Peng,
2021). The organic matter in the top division are
mainly in the form of OMA and were interpreted to
be derived from marine algae and associated with pri-
mary productivity (Macquaker et al., 2010).
The enrichment of RSTEs in sea-level lowstand
anoxic siliceous mudrocks may be attributed to
increased basin restriction and subsequent anoxic ben-
thic conditions (Peng et al., 2021). These seawater sol-
uble and conservative oxidation states of RSTEs will
transfer into insoluble particle-reactive forms under a
reducing environment and scavenged from the seawa-
ter (Tribovillard et al., 2006; Algeo and Tribovillard,
PENG AND LARSON 453
 2009). Furthermore, some specific RSTEs, such as
Mo, Ni, Cu, Zn, and V, are predominantly delivered
to the sediments in association with organic matter in
the form of organometallic complexes under anoxic
conditions (e.g., Helz et al., 1996; Tribovillard et al.,
2004; Algeo and Tribovillard, 2009). Thus, the pres-
ence of the high abundance of OMA in the homoge-
nized top division of anoxic siliceous mudrocks (Fig-
ure 9D) will further contribute to the enrichment of
some specific RSTEs. An alternate hypothesis for the
enrichment of RSTEs in this chemofacies is that the
RSTEs may be concentrated within rip-up clasts (Fig-
ure 9C) that were transported from other parts of the
slope or shelf environment. However, these rip-up
clasts (Figure 9C) lack organic matter, which is the
necessary substance for the scavenge of RSTEs from
the seawater. Furthermore, the contemporary shelf
and slope environment should have been character-
ized by less reducing conditions compared to the basin
floor. Thus, the authors suggest this hypothesis is less
likely to have happened.
Oxic-Suboxic Intrabasinal Carbonates
The oxic-suboxic intrabasinal carbonates are enriched
in Ca and Mg but depleted in RSTEs and detrital
proxies (Figures 5–7). The high content of Ca and
Mg in this chemofacies is believed to reflect the high
abundance of biocalcareous allochems and euhedral
dolomite cement (Figure 10). Extremely low Zr and
Ti content and widespread dolomite cementation
suggest limited detrital input during the deposition of
oxic-suboxic intrabasinal carbonates, which has been
interpreted as rising sea level and retrogradation of sil-
iciclastic systems on the Eastern shelf in previous
studies (Brown et al.,1990; Peng, 2021; Peng et al.,
2021). Based on petrographic observation, the pri-
mary grain assemblages in oxic-suboxic intrabasinal
carbonates, such as radiolarians, calcispheres, peloids,
and conodonts (Figure 10F–H), mainly originated
from the water column (Peng, 2021). Moreover,
minor shallow-water carbonate bioclasts (e.g., Figure
10E) derived from the carbonate platform developed
on the Eastern shelf during this period were deposited
through gravity flows (Schlager et al., 1994; Peng,
2021). A low concentration of RSTEs suggests overall
oxic-suboxic bottom water conditions.
Based on the established stratigraphic framework
by Peng (2021), the oxic-suboxic intrabasinal
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carbonates are interpreted to have been deposited
during sea-level highstand. Siliciclastic transportation
systems were trapped behind the carbonate platform
on the shelf area (Figure 2). Meager detrital input
and low sedimentation rate favored conditions result-
ing in the widely observed euhedral dolomite cemen-
tation (Figure 10). Suspension fallout and highstand
shedding processes (Schlager et al., 1994) were
responsible for the deposition of pelagic allochems
(Figure 10F, H) and shelf bioclasts (Figure 10E) in
this chemofacies, respectively (Peng, 2021).
It is worth noting that projections of two produc-
tivity proxies (P and Ba) are not in agreement with
each other in Figure 4. Furthermore, no certain rela-
tionships between these two elements and other ele-
ments were observed (Figure 4). A likely reason for
this phenomenon may be caused by remobilization
of P and Ba after deposition (i.e., during the diagene-
sis stage). It has been reported that P and Ba in sedi-
ments could be dissolved into pore water in anoxic
(presence of sulfide) conditions and diffuse upward
from sediment and finally returned to the seawater
(Brumsack and Gieskes, 1983; Paytan et al., 1993,
2002; Ingall and Jahnke, 1994; Tribovillard et al.,
2006). In previous cases reported by Benitez-Nelson
(2000), as much as 99% of organic P may be released
from organic matter decay in anoxic (presence of
sulfide) conditions and then back into the water col-
umn. Thus, although high primary marine productiv-
ity occurred, Ba and P were not necessarily enriched
in sediments where benthic conditions are anoxic
(Tribovillard et al., 2006). In addition, some authi-
genic minerals (e.g., apatite and barite) that filled
fractures of the Cline Shale and formed some specific
nodules (e.g., barite and phosphate nodule) linked to
biological reactions (Lash, 2015) may also likely have
caused some unusual Ba and P enrichment pattern.
In addition, the Ba enrichment pattern in the core
samples may also likely be affected by drilling fluid.
Evolution of Bulk Petrophysical and Rock
Mechanical Properties
Oxic-Suboxic Detrital-Enriched Argillaceous
Mudrocks
This clay matrix-rich chemofacies (Figure 8) can be
easily mechanically compacted during the diagenetic
process, and thus, rare intergranular or intragranular
 pores can be preserved (Milliken et al., 2012;
Milliken, 2014). Reed and Roush (2016) and Peng
et al. (2020b) indicate that very limited intragranular
and intergranular pores can be observed from these
clay matrix-rich samples of the Cline Shale because
of intensified mechanical compaction. In agreement
with previous studies, relatively low bulk crushed-
rock porosity (median: 1.22%) and permeability
(median: 7.6 · 10 5 md) were detected in the oxic-
suboxic detrital-enriched argillaceous mudrocks in
this study (Figure 11B, C).
Furthermore, rigid grains (generally <10 vol. % of
quartz, feldspar, and carbonate grains based on petro-
graphic estimation) in the oxic-suboxic detrital-
enriched argillaceous mudrocks are “floating” in the
ductile clay matrix (Figure 8D). These rigid grains do
not form a touching framework (Figure 8D). As a
result, compaction stress can be accommodated and
absorbed by particle rearrangement within the duc-
tile clay matrix (Milliken et al., 2018). This inference
is consistent with the lowest bulk UCS (median: 494
HLD) of oxic-suboxic detrital-enriched argillaceous
mudrocks as reported in this study (Figure 11D).
Anoxic Siliceous Mudrocks
The anoxic siliceous mudrocks are characterized
by volumetrically significant rigid grains (e.g., silt
quartz, feldspar, calcite, and biosilicoeus allochems;
Figure 9). These rigid grains are likely to form a
touching framework, which could increase rock brit-
tleness by creating force chains that pass through
rigid grain contacts (Daniels and Hayman, 2008;
Emmings et al., 2020; Peng et al., 2020a). This infer-
ence is consistent with the relatively high bulk UCS
(median: 586 HLD) detected in the anoxic siliceous
mudrocks (Figure 11D).
The highest bulk crushed-rock porosity (median:
2.04%) and permeability (median: 1.53 · 10 4 md)
of anoxic siliceous mudrocks (Figures 11B, C) are
likely caused by three factors. First of all, the touch-
ing framework of rigid grains will contribute to the
preservation of intergranular pores by creating pack-
ing flaws below those contacts during mechanical
compactions (Schneider et al., 2011). Second, the
early dissolution of chemically unstable biosiliceous
allochems and precipitation of matrix dispersed
authigenic microquartz in the anoxic siliceous
mudrocks as identified by Peng et al. (2020a) will
suppress pore collapse (i.e., “buttress effect”;
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Emmings et al., 2020) and retaining the pore space.
Finally, the Cline Shale is dominated by organic
matter-hosted pores (Reed and Roush, 2016; Peng
et al., 2020a), and thus, the higher concentration of
organic matter in anoxic siliceous mudrocks will
increase the bulk porosity and permeability.
Oxic-Suboxic Intrabasinal Carbonates
Widely distributed carbonate cement (Figure 10) in
oxic-suboxic intrabasinal carbonates acts as a binder
of other rigid grains and significantly increases rock
brittleness (medium UCS: 776 HLD; Figure 11D).
However, this widely distributed cement also causes
a dramatic decrease of bulk porosity (median: 0.7%)
and permeability (median: 6.9 · 10 5 md) (Figures
11B, C).
Mechanisms for Organic Matter
Enrichment
In general, the highest bulk TOC was detected in
anoxic siliceous mudrocks (Figure 11A), suggesting
an overall redox control on bulk TOC enrichment.
The falling sea level (>100 m glacioeustatic falls dur-
ing the Late Pennsylvanian; Rygel et al., 2008) during
the deposition of anoxic siliceous mudrocks would
have resulted in the severe isolation of the Midland
Basin from open marine waters (Panthalassic ocean
in Figure 1) (Nance and Rowe, 2015; Peng et al.,
2021). This increased basin restriction can result in
stratified water-column and consistent anoxic bot-
tom water conditions, which were favorable for
organic matter preservation in deep basins along the
Great Permian seaway (Nance and Rowe, 2015;
Peng et al., 2021). A similar organic matter enrich-
ment pattern (i.e., high TOC successions deposited
during sea-level lowstand with increased basin
restriction) was also reported in the lower Permian
mudrock successions in the Delaware Basin (west of
the Midland Basin; Figure 1) by Nance and Rowe
(2015).
Although anoxic siliceous mudrocks contain the
highest bulk TOC (Figure 11A), organic matter is
not homogeneously distributed throughout the rock
matrix. Based on SEM observation, organic matter in
the anoxic siliceous mudrocks are almost exclusively
in the form of OMA (Macquaker et al., 2010) and
only enriched in the homogenized top division of
anoxic siliceous mudrocks (Figure 9D). The OMA
PENG AND LARSON 455
 was interpreted to have originated from primary
algae blooms delivered to the seafloor as suspension
fallout (“marine snow” of Macquaker et al. [2010]).
The interlaminated fabric of erosive basal silt-sized
particle-rich division (distal turbidite; Peng, 2021)
and organic-rich homogenized top division (pelagic
deposits; Peng, 2021) indicates a highly variable and
dynamic depositional process and environment for
the organic-rich anoxic siliceous mudrocks. Similar
millimeter-scale interlaminated fabric (i.e., interlami-
nated turbidite and organic-rich pelagic deposits) was
also identified in many other marine shale systems,
such as Whitby Mudstone Formation, Yorkshire
Coast, England, Kimmeridge Clay Formation, Kim-
meridge Bay, England, and Hue Shale, North Slope
of Alaska (Macquaker et al., 2010). These discoveries
challenge the conventional model that organic-rich
mudrocks are deposited by background “rainout” in a
consistent quiescent environment with rare detrital
input.
“Sweet Spot” for Shale Oil Production in the
Cline Shale
The oxic-suboxic detrital-enriched argillaceous
mudrocks are characterized by moderate to low bulk
TOC (median <2 wt. %). In addition, the low poros-
ity (median: 1.22%) and permeability (median: 7.5 ·
10 5 md) of the oxic-suboxic detrital-enriched argil-
laceous mudrocks (Figure 11) are unfavorable for oil
enrichment. The low UCS (median: 494 HLD;
Figure 11) of oxic-suboxic detrital-enriched argilla-
ceous mudrocks suggests a ductile mechanical prop-
erty, which is unfavorable for hydraulic fracturing
and oil production. Thus, the detrital-enriched argil-
laceous mudrocks are unlikely to be the sweet spot
for industrial shale oil production, consistent with
the results of previous industrial exploration drilling
(Jacobs, 2013) and the well-known low value of duc-
tile mudrocks as shale hydrocarbon reservoirs.
The oxic-suboxic intrabasinal carbonates are
characterized by the highest UCS (median: 777
HLD; Figure 11), suggesting a rigid mechanical prop-
erty and favorable for oil production. However, the
oxic-suboxic intrabasinal carbonates are also charac-
terized by the lowest TOC (median: 0.5 wt. %;
Figure 11), suggesting limited hydrocarbon genera-
tion potential and, thus, unfavorable for in situ oil
enrichment. Furthermore, the extremely low poros-
ity (median: 0.7%) and permeability (median: 6.9 ·
456 Approach for Mudrock Chemofacies Characterization
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10 5 md), caused by wide dolomitic cementation
throughout the rock matrix, are unfavorable for oil
enrichment in this chemofacies. The Rock-Eval data
sets of the Cline Shale from Zheng (2016) suggest
that oxic-suboxic intrabasinal carbonates are charac-
terized by the lowest amount of hydrocarbon that
can be volatilized from the rock (S1)/TOC compared
to the other two chemofacies, indicating limited free
hydrocarbon in this chemofacies. Thus, the oxic-
suboxic intrabasinal carbonates are also unlikely to be
the sweet spot for shale oil production.
The anoxic siliceous mudrocks are characterized
by the highest bulk TOC (median: 5 wt. %), mod-
erate to high UCS (median: 586 HLD), the highest
porosity (median: 2.04%), and the highest perme-
ability (median: 1.5 · 10 4 md; Figure 11), indicating
relatively good hydrocarbon generation potentials,
hydrocarbon enrichment capacity, and reservoir frac-
turing conditions. The anoxic siliceous mudrocks also
exhibit the highest S1/TOC among the other two
chemofacies (Zheng, 2016), suggesting a relatively
high concentration of free hydrocarbon in this che-
mofacies. Thus, we suggest the anoxic siliceous
mudrocks of the Cline Shale are the most favorable
sweet spot for shale oil production.
Implications for Industrial
Unconventional Resources Exploration
The ED-XRF elemental measurement is not destruc-
tive for core samples and provides an efficient and
cost-saving way to obtain large multivariate data sets
as needed in mudrocks research. These elemental
compositions contain information of mineral compo-
sition (Al, Si, K, Na, Mg, Ca), detrital input (Rb, Th,
Ti, and Zr), redox condition (Co, Cr, Cu, Mo, Ni,
Pb, U, V, and Zn), and paleoproductivity (Ba and P),
which can be linked to a certain deposition environ-
ment and composition of primary grain assemblages.
Moreover, the primary grain assemblages in the
mudrocks further determined potential diagenetic
pathways and evolution of bulk petrophysical and
mechanic properties (Milliken et al., 2012; Milliken
2014; Peng et al., 2020a, b). Thus, rocks character-
ized by significantly different bulk elemental
compositions (i.e., different chemofacies) are always
correlated to different bulk mineral compositions,
TOC, UCS, porosity, and permeability as shown in
this study.
 Figure 12. Stratigraphical proportions of each chemofacies of the Cline Shale. Note that the anoxic siliceous mudrocks, which are most
favorable for shale oil production, only account for 21% stratigraphic volume of the Cline Shale.
The PCA and k-means clustering are important
and efficient enough to classify ED-XRF measure-
ments typical in a big database (e.g., 5000 ED-XRF
measurements; each measurement contains 25 major
and trace elements in this study). This approach effi-
ciently delineates the anoxic siliceous mudrocks as
the sweet spots for shale oil production, which only
account for minor stratigraphic volume (21%) of the
entire Cline Shale (80 m thick in the study area;
Figure 12). This rapid, economic, and effective inte-
grated approach for chemofacies characterization
proposed here informs a new idea to discriminate
favorable sweet spots for the Cline Shale as well as
other shale systems in industrial unconventional
exploration.
CONCLUSIONS
The ED-XRF-derived elemental composition con-
tains information of mineral composition (Al, Si, K,
Na, Mg, Ca), detrital input (Rb, Th, Ti, and Zr),
redox condition (Co, Cr, Cu, Mo, Ni, Pb, U, V, and
Zn), and paleo-productivity (Ba and P). The PCA
and k-means clustering analyses of 25 elements from
core-based ED-XRF measurements help minimize
the number of components necessary to describe all
these element variations in a big database and effi-
ciently discriminate different chemofacies. This novel
integrated protocol for chemofacies characterization
as demonstrated by the Cline Shale in this study is
cost-effective, efficient, and nondestructive to core
samples, which exhibits huge potential for wide
applications in industrial unconventional resources
exploration.
Using this approach, three chemofacies, includ-
ing oxic-suboxic detrital-enriched argillaceous
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mudrocks, anoxic siliceous mudrocks, and oxic-
suboxic intrabasinal carbonates, were identified from
the Cline Shale. The stratigraphically minor anoxic
siliceous mudrocks that are characterized by high
TOC, UCS, porosity, and permeability are inter-
preted as the most favorable target for shale oil pro-
duction. Anoxic benthic conditions are likely the
dominant factors controlling bulk TOC enrichment.
Interlaminated fabrics in the anoxic siliceous
mudrocks suggest a highly variable depositional envi-
ronment, which challenged the traditional view that
organic-rich mudrocks were deposited in a consis-
tently deep and quiet environment.
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