Marine and Petroleum Geology 120 (2020) 104569

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Marine and Petroleum Geology

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Research paper

Mineralogy and element geochemistry of salinized lacustrine organic-rich

shale in the Middle Permian Santanghu Basin: Implications for
paleoenvironment, provenance, tectonic setting and shale oil potential
Bo Liu a, Yu Song b, c, *, Kai Zhu b, Peng Su b, Xiang Ye b, Wanchun Zhao a
a
Accumulation and Development of Unconventional Oil and Gas, State Key Laboratory Cultivation Base Jointly-constructed by Heilongjiang Province, Ministry of Science
and Technology, Northeast Petroleum University, Daqing, 163318, China
b
Key Laboratory of Tectonics and Petroleum Resources (China University of Geosciences), Ministry of Education, Wuhan, 430074, China
c
Key Laboratory of Mineral Resources Evaluation in Northeast Asia, Ministry of Natural Resources, Changchun, 130061, China

A R T I C L E I N F O A B S T R A C T

Keywords: The Middle Permian Lucaogou Formation in the Santanghu Basin (northwest China) develops one of the thickest
Shale oil potential salinized lacustrine organic-rich shale (SLORS) in the world. The SLORS has been proven as sources for crude oil
Provenance and tectonic setting and tight oil, as well as sources and reservoirs for shale oil in the basin. A total of 52 SLORS samples were
Salinized lacustrine organic-rich shale (SLORS)
collected from the second member of Lucaogou Formation (P2l2), and analyzed by mineralogy and element
Middle permian
Northwest China
geochemistry, in order to reveal the paleoenvironment, provenance, tectonic setting and shale oil potential. The
results imply an evolution of paleoenvironment from anoxic, saline to dysoxic-oxic, freshwater lake, which is
caused by an increased freshwater influx. Early in the P2l2, volcanic ash and hydrothermal fluids have increased
the nutrient level in the lake and therefore elevated the bioproductivity. The P2l2 SLORS is originated from
intermediate volcanic rocks, accompanied by minor proportions of basic volcanic rocks. The parent rocks of P2l2
SLORS have experienced weak degree of chemical weathering, and probably derived from a continental island
arc setting. Micro-, nano-pores (inter-grain pores, inter-crystalline pores, dissolution pores and organic matter
pores) and microfractures are widely observed in the P2l2 SLORS, which provides sufficient storage space for
hydrocarbons. The P2l2 SLORS is dominated by carbonate minerals, quartz and feldspar, which are all brittle
minerals and favourable for artificial fracturing. Comprehensive study indicates that the upper P2l2 SLORS hosts
a better shale oil potential, due to the relatively high TOC, abundant micropores and microfractures, and high
brittle mineral contents. In addition, individual element geochemical parameters in the Santanghu Basin should
be used with caution, for example, the paleoredox proxy U/Th and paleosalinity proxy Sr/Ba are also influenced
by volcanic and hydrothermal activity. This implies that a multi-proxy analysis should be applied during the
study of paleoenvironmental conditions.

1. Introduction
Shale is defined as a fine-grained sedimentary rock that exhibits
fissility and a more general classification of mudstone (Aplin and Mac­
quaker, 2011). Organic-rich shale refers to the shale with elevated total
organic carbon contents (generally TOC > 2.0%; Hosterman and
Whitlow, 1980), which commonly acts as important petroleum sources,
reservoirs for shale oil and gas, and seals in conventional reservoirs
(Jarvie et al., 2007; Abouelresh and Slatt, 2012; Liang et al., 2018).
Organic-rich shale are widespread in salinized lacustrine basins
throughout China, such as the Middle Permian Lucaogou Formation in
Junggar and Santanghu basins in northwest China (Carroll, 1998; Liu
et al., 2017), the Upper Jurassic Yanchang Formation in Ordos Basin in
central China (Zhang et al., 2020), the Upper Cretaceous Qingshankou
and Nenjiang formations in Songliao Basin in northeast China (Bechtel
et al., 2012), and the Eocene Shahejie Formation in Bohai Bay Basin in
east China (Liang et al., 2017, 2018). These salinized lacustrine
organic-rich shale (SLORS) have been proven as crucial source rocks for
conventional oil, as well as sources and reservoirs for unconventional oil
(Wang et al., 2019).
The SLORS developed in the Middle Permian Lucaogou Formation
(P2l) in Junggar and Santanghu basins in northwest China is considered

* Corresponding author. Key Laboratory of Tectonics and Petroleum Resources (China University of Geosciences), Ministry of Education, Wuhan, 430074, China.
E-mail address: songyu@cug.edu.cn (Y. Song).

https://doi.org/10.1016/j.marpetgeo.2020.104569
Received 16 March 2020; Received in revised form 15 June 2020; Accepted 29 June 2020
Available online 2 July 2020
0264-8172/© 2020 Elsevier Ltd. All rights reserved.
B. Liu et al.
as a ‘‘world class source rock’‘, due to its favourable thickness and
organic-richness (Carroll, 1998; Liu et al., 2018a). In the Santanghu
Basin, the P2l SLORS has been proven as hydrocarbon sources for crude
oil (the Jurassic sandstone) and tight oil (the Permian Tiaohu Forma­
tion), as well as sources and reservoirs for shale oil (the P2l; Ge et al.,
2015; Liu et al., 2015; Ma et al., 2016). Previous studies on P2l SLORS in
the Santanghu Basin mainly focused on the volcanic-hydrothermal
sedimentation (Wen et al., 2009, 2013; Li et al., 2012a, b; Liu et al.,
2010, 2012, 2013; Li and Yao, 2016; Jiao et al., 2018a, b, 2020), pale­
oenvironmental conditions (Hackley et al., 2016; Liu et al., 2017, 2018a;
Zhang et al., 2018), lithofacies (Liu et al., 2018b) and oxygen-bearing
geolipids (Wang et al., 2016). However, relatively few researches have
been conducted on the provenance and tectonic setting of P2l SLORS in
the Santanghu Basin (Tao et al., 2017). In addition, due to the strong
heterogeneity of SLORS (Kelts, 1988), the results of paleoenvironmental
conditions are often highly varied with the sampling locations (e.g.
Hackley et al., 2016; Liu et al., 2017). Thus, further study is still needed
to reveal the paleoenvironment of P2l SLORS in the Santanghu Basin.
Shale mainly composed of mixture of fine-grained quartz and clay
minerals, and also include other minerals such as feldspar, carbonate
minerals, sulfide minerals and oxide minerals (Slatt and Rodriguez,
2012; Chermak and Schreiber, 2014). Ternary diagram of clay minerals,
quartz and feldspar, and carbonate minerals could be used to indicate
depositional environment and tectonic setting (Lev et al., 2008; Boggs,
2001). Clay minerals in shale is dominated by illite, mixed layer illi­
te/smectite, smectite, kaolinite and chlorite (Aplin and Macquaker,
2011). The composition of clay minerals in shale is jointly influenced by
provenance (the nature of parent materials), paleo-weathering, burial
diagenesis and hydrothermal alteration (Chermak and Rimstidt, 1990;
Deer et al., 2013).
Fig. 1. (a) Location of the Santanghu Basin; (b) geological map of the Santanghu Basin and the sampling well; (c) simplified distribution of the Lucaogou Formation;
(d) stratigraphic section of the Upper Carboniferous-Permian strata in the Santanghu Basin (after Liu et al., 2017, 2018a).
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Marine and Petroleum Geology 120 (2020) 104569
Element concentrations and/or ratios in organic-rich shales have
been utilized for interpretation of paleoenvironmental conditions during
shale deposition (Tribovillard et al., 2006; Ross and Bustin, 2009; Song
et al., 2020). Recently, several reviews have been made on the use of
concentrations and/or ratios of element for paleoredox (Co, Cr, Mo, U, V
and Re) and paleosalinity (Sr, Ba, B, Ga and S) indicators (Wei and
Algeo, 2019; Algeo and Liu, 2020; Bennett et al., 2020). Some immobile
elements, including La, Th, Co, Sc, Ni, Zr and Y, reveal different con­
centrations and/or ratios from different parent rocks and tectonic set­
tings (Cullers and Berendsen, 1998; Cullers, 2002). Thus, the cross and
ternary diagrams of these immobile elements could be used to distin­
guish the provenance and tectonic setting of shale (Saminpanya et al.,
2014; Moradi et al., 2016; Tao et al., 2016, 2017; Verma and
Armstrong-Altrin, 2016; Deng et al., 2019).
In this paper, mineralogy and element geochemistry of P2l SLORS in
the Santanghu Basin were analyzed by X-ray diffraction (XRD), X-ray
fluorescence spectrometry (XRF), inductively coupled plasma-mass
spectrometry (ICP-MS) and scanning electron microscope (SEM), in
order to shed light on paleoenvironmental conditions, provenance and
tectonic setting. Furthermore, a combination of organic geochemistry
(Liu et al., 2017, 2018a) and reservoir characteristics was applied to
indicate the shale oil potential of P2l SLORS. In particular, we focus on
the comparison of paleoenvironment results obtained from element
concentrations (and ratios) and organic parameters (e.g. pristane/phy­
tane, gammacerane index; Liu et al., 2017) to assess the validity of these
paleoenvironmental indicators.
2. Geological setting
The Santanghu Basin is located in the east of Junggar Basin, the north
B. Liu et al.
of Turpan-Hami Basin, the south and west of the Republic of Mongolia
(Fig. 1a). The basin can be subdivided into three tectonic units from
southwest to northeast are Southwest Thrust Nappe Belt, Central
Depression Belt and Northeast Thrust Nappe Belt (Liu et al., 2017). The
Central Depression Belt comprises four sags, from northwest to south­
east are Hanshuiquan Sag, Tiaohu Sag, Malang Sag and Naomaohu Sag,
of which the Malang Sag, with an area of approximately 1800 km2
(Fig. 1b), has been relatively well explored and was selected as the target
area of this study.
The Santanghu Basin develops a Permian succession which is
composed of the Lucaogou Formation (P2l) and the Tiaohu Formation
(P2t) intercalated between the Carboniferous volcanic rocks and the
overlying Jurassic clastic rocks. In the Malang Sag, the thickness of P2l
reveals a decrease trend from the southwest to northeast with a
maximum thickness of 600 m (Fig. 1c). The thickness distribution of P2l
is probably related to the pre-Jurassic erosion (Liu et al., 2017). The P2l
mainly comprises mudstone, calcareous mudstone, tuffaceous
mudstone, carbonate rocks and other fine-grained sediments, which is
representative of a lacustrine, mixed carbonate- and volcanic-clastic
sedimentary succession (Fig. 1d). Based on the lithological assemblage
and geophysical characteristics, the P2l can be further divided into three
members, from bottom to top are first member (P2l1), second member
(P2l2) and third member (P2l3) (Fig. 1d). Thick organic-rich shale was
deposited in the P2l2 interval, which was considered as main source
rocks for both conventional and unconventional hydrocarbons in the
basin (Ma et al., 2016; Liu et al., 2018a). Therefore, the P2l2 was selected
as the target layer of this study.
Based on the lithological association, the studied P2l2 succession is
subdivided into three units (Fig. 2). The lower Unit I is dominated by
tuffaceous mudstone interbedded with breccia, dolostone, dolomitic
mudstone and fine sandstone. The middle Unit II is mainly composed of
mudstone, lime mudstone, dolomitic mudstone, dolostone and tuffa­
ceous mudstone. The upper Unit III primarily consists of lime mudstone,
dolomitic mudstone, mudstone and dolostone.
3. Samples and methods
A total of 52 samples from the P2l2 were collected from an explora­
tion well in the northwest of Malang Sag, Santanghu Basin (Fig. 1b). All
samples have been performed on X-ray diffraction (XRD), X-ray fluo­
rescence spectrometry (XRF) and inductively coupled plasma-mass
spectrometry (ICP-MS) analyses. Based on these results, samples with
different mineral compositions were selected for scanning electron
Fig. 2. Vertical variations of mineral compositions in the P2l2 organic-rich shale.
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Marine and Petroleum Geology 120 (2020) 104569
microscopic (SEM) analysis.
For XRD analysis, samples were dried by isopropanol after removal
of drilling contaminations. After the pre-treatment, pulverized samples
were dispersed in a dilute sodium phosphate solution using a sonic
probe, which represents random whole-rock mounts. Clay composition
was analyzed by clay-size (<4 μm ESD) fraction obtained from the
suspension by centrifugation and vacuum-deposition of the remaining
suspension on silver membrane filters. Mineral composition was deter­
mined by a Bruker AXS D80-Focus instrument, with scanning step length
of 0.01。2θ. Qualitative and semi-quantitative interpretations of raw
results were performed on the Jade software.
Based on the results of XRD analysis, samples with different mineral
compositions were selected for regular SEM and Ar-ion milled SEM
analyses, in order to study the morphology of minerals/organic matter,
(micro-) pore/fracture characteristics and their filling constituents. For
regular SEM analysis, the polished sections of samples were gold coated
for conductivity by a Quorum Q150T ES sputtering coater. For Ar-ion
milled SEM analysis, the representative cubes of the samples were pol­
ished using an argon ion mill in order to obtain an extremely flat,
artefact-free surface fits for analysis with back scattered electrons (BSE).
The SEM analysis was performed on a FEI Quanta™ 650 FEG scanning
electron microscope. In addition, an energy dispersive spectrometer
(EDS) system (SDD Inca X-Max 50) was applied to indicate the elemental
compositions of observed minerals.
The contents of major-element oxides (including SiO2, Al2O3, Fe2O3,
CaO, Na2O, K2O, MgO, TiO2, P2O5 and MnO) of samples were deter­
mined by XRF analysis using a Bruker Advanced X-ray Solutions S4
Pioneer instrument. Samples were pre-heated in a muffle furnace (815
�
C) to determine the loss on ignition (LOI). After that, the residuals were
mixed with lithium tetraborate and prepared as pressed powder mounts
for subsequent XRF analysis. To determine the concentrations of trace
elements in samples, a Thermo Scientific X series II high-resolution
inductively coupled plasma-mass spectrometer (HR-ICP-MS) was used.
Before the HR-ICP-MS analysis, the homogenous pulverized samples
were digested using a mixture of 2-ml HNO3 (65% v/v) and 5-ml HF
(40% v/v). The analytical reliability was guaranteed by standard ma­
terials (AGV-2, RGM-2; Schudel et al., 2015) and duplicate analyses.
4. Results
4.1. Mineralogy
Vertical distribution of minerals through the P2l2 interval are
B. Liu et al.
illustrated in Fig. 2, and the corresponding data are provided in Sup­
plementary Table 1. Dolomite (and Fe-dolomite; avg. 31.7%) is the
predominant mineral in the P2l2 SLORS, followed by quartz (avg.
24.0%), plagioclase (avg. 18.7%), clay minerals (avg. 11.2%), K-feldspar
(avg. 5.6%), calcite (avg. 5.2%) and pyrite (avg. 3.4%). In addition,
trace amounts of siderite, magnesite, barite, apatite, fluorite, marcasite
and analcime were observed in the P2l2 SLORS (Fig. 3). The three units,
as outlined above, are also recognizable in the mineral composition
(Fig. 2). Moreover, based on variations in clay minerals, the middle Unit
II can be further subdivided into two parts, the lower Unit II1 is domi­
nated by smectite and illite & mica, whereas the upper Unit II2 is mainly
composed of mixed layer illite/smectite (Fig. 2).
4.1.1. Quartz
Quartz content is relatively low in the Unit I (avg. 18.4%), but
abundant in the Unit II1 (avg. 24.7%), II2 (avg. 28.2%) and III (avg.
23.1%; Fig. 2). Quartz occurred in both authigenic and detrital in the
P2l2 SLORS. The authigenic quartz is mainly occurred as microcrystal­
line quartz concretions (or chert; Liu et al., 2018a). They are mainly
derived from low-temperature hydrothermal fluids, as evidenced by the
characteristics of fluid inclusions therein (Jiao et al., 2020). The detrital
quartz is generally 5–10 μm in size with sub-angular to sub-rounded
shape (Fig. 3). Smooth surfaces are generally observed in the detrital
quartz grains, which reveals that they have carried as suspension load
without major collision during the short-distance transport.
4.1.2. Feldspar
Feldspar is composed of K-feldspar and plagioclase in the P2l2 SLORS.
K-feldspar is enriched in the Unit I (avg. 6.5%), II1 (avg. 8.8%) and II2
(avg. 7.0%), but completely missing in the Unit III (avg. 0.7%; Fig. 2).
The K-feldspar is 4–20 μm in size, sub-angular to sub-rounded shape, and
mainly occurs as framework grains and interstitial grains (Fig. 3), which
probably indicates intense fragmentation and short-distance transport.
However, minor proportions of K-feldspar are probably of igneous
origin, which is presented as orthoclase core surrounded by albite, or the
orthoclase and albite are in sutured contact, as indicated in Jiao et al.
(2020). The content of plagioclase reveals an upward increasing trend,
with relatively low content in the Unit I (avg. 4.5%) and relatively high
content in the Unit III (avg. 27.3%; Fig. 2). The plagioclase is 1–5 μm in
size, sub-angular to sub-rounded shape, and occurs in fractures in the
shale, which suggests intense fragmentation and short-distance
transport.
4.1.3. Carbonate minerals
Carbonate minerals in the P2l2 SLORS comprise calcite, dolomite and
minor amounts of magnesite. The amount of calcite is relatively low in
samples except in the Unit III (~47.3%; Fig. 2). The calcite mainly oc­
curs as sub-rounded shape. Dolomite (and Fe-dolomite) is the dominant
carbonates with contents ranging from 1.5 to 75.4% (avg. 31.7%; Fig. 2).
The dolomite (and Fe-dolomite) particles are 8–50 μm in size, and Fe is
generally concentrated in the center of the particle (Fig. 3a). The dolo­
mite in the P2l of Santanghu Basin is probably derived from mantle-
originated hydrothermal fluids, as evidenced by 87Sr/86Sr ratios (Liu
et al., 2012).
4.1.4. Clay minerals
Clay minerals in the P2l2 SLORS includes smectite, interstratified
illite-smectite (I/S) and illite & mica (I&M) with varying amounts.
Smectite is relatively abundant in the Unit I and the upper part of Unit
II1, with contents up to 58.6%, whereas the I/S (avg. 4.3%) and I&M
(avg. 3.1%) show slightly higher contents in the Unit II2 and III (Fig. 2).
Smectite is probably formed by alteration of basic volcanic rocks or
volcanic ash in lake water (Gill, 2010). Therefore, the abundance of
smectite in the Unit I and the upper part of Unit II1 is probably indicative
of volcanic activity near lake during the deposition of these intervals.
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Marine and Petroleum Geology 120 (2020) 104569
4.1.5. Other minerals related to volcanic and hydrothermal activity
Pyrite is occasionally observed in the P2l2 SLORS, with contents
varying between 0.6 and 15.6% (avg. 2.8%; Fig. 2). Pyrite occurs in
idiomorphic forms and framboidal aggregates in the shale (Fig. 3a),
probably indicating a syngenetic origin. A portion of idiomorphic pyrite
is likely to derive from hydrothermal fluids, because volcanoclastic
sediments were found in the vicinity of the basin (Inner Mongolia
Wulantuga; Dai et al., 2012), whereas the framboidal pyrite is related to
the oxygenation state of paleoenvironment (Wilkin et al., 1996). In
addition, minor proportions of fracture-filled epigenetic pyrite are also
observed in the P2l2 SLORS (Liu et al., 2018a).
Clay-to silt-sized, sub-angular to sub-rounded barite was observed
within fractures in the P2l2 SLORS, together with quartz, K-feldspar and
plagioclase (Fig. 3b). Barite could be formed by multiple processes,
including biogenic, hydrothermal and evaporation (Hanor, 2000; Dai
et al., 2014). The barite in the shale is likely to associate with hydro­
thermal process, because of the presence of hydrothermal minerals in
the P2l2 SLORS. Apatite in the P2l2 SLORS generally occurs as euhedral
grains (Fig. 3c), which is indicative of volcanic input (Dai et al., 2017
and references therein). Fluorite grains in the P2l2 SLORS commonly
display relict K-feldspar after replacement (Fig. 3d), suggesting that the
mineral was probably formed by hydrothermal fluids alteration (Dai
et al., 2013).
The position of P2l2 SLORS in the ternary diagram (based on relative
proportions of clay minerals, carbonates, quartz and feldspar) reveals
that the variability of mineral compositions in shales (Fig. 4). Relatively
high proportions of clay minerals (mostly smectite) are observed in the
Unit I and II1, whereas high proportions of carbonates, quartz and
feldspar are present in the Unit II2 and III. In comparison, the P2l2 SLORS
from Shitoumei Salient of Santanghu Basin reveals a less variable and
carbonates-dominated mineral composition (Fig. 4; Tao et al., 2017).
4.2. Element geochemistry
The three units, as identified by lithological association and mineral
composition, is also recognizable in the major and trace element con­
centrations (Fig. 5, Fig. 6).
4.2.1. Major-element oxides
Major-element oxides, including SiO2, Al2O3, Fe2O3, CaO, Na2O,
K2O, MgO, TiO2, P2O5 and MnO are detected in the P2l2 SLORS. Among
them, the contents of CaO and MgO are much higher than the upper
continental crust (UCC; data from McLennan, 2001), the contents of
SiO2, Na2O and K2O are slightly higher than the UCC, whereas the
contents of Al2O3, Fe2O3, TiO2, P2O5 and MnO are lower than the UCC
(Fig. 5; Supplementary Table 2).
Relatively high contents of CaO and MgO are probably related to the
high carbonate minerals in the P2l2 SLORS, as evidenced by positive
correlations between CaO, MgO and calcite, dolomite (and Fe-dolomite;
Fig. 2; Fig. 6a and b). However, minor proportion of CaO may also occur
in other forms such as apatite and fluorite (Fig. 3c and d). As clay
minerals contents are generally low in the P2l2 SLORS (Fig. 2), the SiO2,
Na2O and K2O are mainly occurred in quartz, K-feldspar and plagioclase.
The correlation coefficients between elements can reveal the element
affinity, although these kinds of affinities should be used with caution
(Eskanazy et al., 2010). The correlation coefficients (r) between Al2O3,
TiO2 and SiO2, Na2O are relatively high (0.75–0.90; Supplementary
Table 3), suggesting Al and Ti are probably occurred in quartz and
feldspar, as further supported by the SEM-EDS analysis.
4.2.2. Trace elements
Only Li, Sr, Mo and Sb show higher concentrations in the P2l2 SLORS
in comparison of UCC (Fig. 5; Supplementary Table 2). A strong positive
correlation is observed between Li and MgO (Fig. 6b and c; Supple­
mentary Table 3), which reveals that Li probably hosted in Mg-bearing
minerals, such as dolomite (and Fe-dolomite) and magnesite (Fig. 3a).
B. Liu et al. Marine and Petroleum Geology 120 (2020) 104569

Fig. 3. SEM images and EDS data of crystalline phases of representative samples.

5
B. Liu et al. Marine and Petroleum Geology 120 (2020) 104569

the low concentrations of Mo and Sb, the occurrence modes of these two
elements still remain unclear in the P2l2 SLORS. In addition, no obvious
correlations (r > 0.50) are observed between Mo, Sb and other elements
(Fig. 6e and f; Supplementary Table 3).

4.2.3. Rare earth elements

The concentrations of rare earth elements (REE) in the P2l2 SLORS
range from 18 to 131 μg/g, with an average of 72 μg/g (Fig. 6g; Sup­
plementary Table 2), which is lower than the UCC (146 μg/g; data from
McLennan, 2001). Light rare earth elements (LREE: La–Eu) are more
enriched in comparison of heavy rare earth elements (HREE: Gd–Lu),
with ΣLREE/ΣHREE varying between 4.3 and 12.4 (avg. 7.6; Supple­
mentary Table 2). The chondrite-normalized REE patterns of all samples
are characterized by sloping LREE and flat HREE trends, accompanied
by weak Eu anomalies (avg. 0.90; Fig. 6h). As coarse-grained minerals
are rarely observed in the P2l2 SLORS (Fig. 2; Fig. 3), the absorption of
fine-grained minerals and organic matter is probably the main occur­
rence mode of REE (Fu et al., 2010). The concentrations of REE posi­
tively correlate with Al2O3 (r ¼ 0.60) and TiO2 (r ¼ 0.64; Supplementary
Table 3), which suggests that REE probably occur in quartz and feldspar.
Fig. 4. Ternary diagram based on clay minerals, carbonates, quartz and feld­
spar of the P2l2 organic-rich shale.
5. Discussions

Strontium strongly correlates with CaO and MgO (Fig. 6a, b, d; Sup­
5.1. Paleoenvironmental reconstruction
plementary Table 3), which suggests that Sr is mainly occurred in car­
bonate minerals. In addition, minor proportion of Sr may also occur in
Paleoenvironment was reconstructed based on element geochemical
strontianite and replace Ba in the barite (Deer et al., 2013). Because of
parameters in this study. In order to evaluate the validity of element

Fig. 5. Concentration coefficient of the samples versus upper continental crust (UCC).

Fig. 6. Vertical variations of elevated major and trace elements (compared with UCC), and the chondrite-normalized REE distribution pattern of each unit.

6
B. Liu et al.
geochemical parameters, the results are compared with the paleo­
environment derived from organic petrographic and organic geochem­
ical analyses, as indicated in Liu et al. (2017, 2018a).
5.1.1. Paleoredox conditions
In the ternary diagram of Fe, TOC and total sulfur, samples deposited
in oxic conditions generally plot along the equivalent line of S/TOC ¼
0.4, whereas samples formed in anoxic conditions usually locate along
the line of S/Fe ¼ 1.15 (Arthur and Sageman, 1994; Dean and Arthur,
1989). The SLORS from Unit I and II plot along a line that intersects the
Fe–S axis at approximately 0.41 and 0.39, respectively (Fig. 7a and b),
suggesting anoxic conditions during deposition of these two units. In
contrast, the SLORS from Unit III cluster around the Fe-TOC axis
(Fig. 7c), probably revealing dysoxic-oxic conditions.
Thorium is relatively stable under oxic conditions, whereas the fix­
ation of aqueous U is promoted by reducing conditions and the existence
of organic matter (in sediment or just below the sediment-water inter­
face; Holland, 1984). Thus, the U/Th ratios are indicative of redox
conditions (Jones and Manning, 1994). However, volcanic and hydro­
thermal activity during the deposition and early diagenesis could also
influence the concentrations of U and Th (e.g. Zhang et al., 2020).
Overall, the U/Th ratios display an upward decreasing trend in the
studied interval, with abnormally high ratios in the Unit I and the upper
part of Unit II1 (Fig. 8). Because an upward increasing trend of Pr/Ph
ratios is observed in the studied interval (Fig. 7a in Liu et al., 2017), the
similar trend of U/Th probably imply a gradual evolution of the redox
conditions from a relatively strong reducing to relatively weak reducing
condition. However, the abnormally high U/Th ratios in the Unit I and
the upper part of Unit II1 may be influenced by volcanic and/or hy­
drothermal activity (Fig. 9a).
5.1.2. Paleosalinity and detrital influx
The Sr/Ba ratios have a positive correlation with salinity in both
modern and ancient lacustrine environments (Wei and Algeo, 2019). An
upward decrease trend of Sr/Ba is observed in the studied interval
(Fig. 8), similar to the vertical variation of gammacerane concentrations
from the same profile (Fig. 7a in Liu et al., 2017). Thus, the upward
decrease trend of Sr/Ba ratios suggesting an evolution from saline to
freshwater lacustrine environment. However, abnormally high Sr/Ba
ratios in the Unit I and the upper part of Unit II1 are probably affected by
volcanic and/or hydrothermal activity (Fig. 9b).
As Al and Ti are mainly occurred in detrital minerals (quartz and
feldspar) of terrigenous origin in the P2l2 SLORS, the contents of Al and
Ti can be used to reveal the detrital influx in this study. Slightly upward
increase trends of Al2O3 and TiO2 are shown in the studied profile
(Fig. 8). The upward increase trends of Al2O3 and TiO2, accompanied by
the upward decrease trend of Sr/Ba ratios, suggesting that the low
salinity during the Unit II2 and III deposition are probably caused by
relatively high freshwater inflow (with detrital influx) into the lake. This
conclusion is supported by a warm-temperate paleoclimate during the
Fig. 7. Ternary diagram based on Fe, TOC and total sulfur (TS) of the samples.
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Marine and Petroleum Geology 120 (2020) 104569
Lucaogou Formation in northwest China (Junggar Basin; Sharps et al.,
1992).
5.1.3. Volcanic and hydrothermal activity
Volcanic activity occurred during deposition of the Unit I and the
upper part of Unit II1, as indicated by the presence of smectite, apatite
and biotite in the shale. Volcanic ash particles are generally coated with
soluble salt materials, which would rapidly release nutrients into the
water and promote the bloom of autotrophic microorganisms in marine
and lacustrine environments (Duggen et al., 2007; Zhang et al., 2017).
During deposition of the Unit I and the upper part of Unit II1, volcanic
ash produced from eruptions may have released a large number of
nutrient elements to the lake surface, which could promote the flour­
ishing of algae and photosynthetic cyanobacterial and increase the
bioproductivity in the lake surface. This conclusion is supported by
relatively high concentrations of steroids, hopanoids, tricyclic terpanes
and β-Carotane in the samples from these intervals (Fig. 7 in Liu et al.,
2017).
The occurrence of hydrothermal activity during deposition of the
Unit I and the upper part of Unit II1 is evidenced by the presence of
authigenic quartz, dolomite (and Fe-dolomite), syngenetic pyrite, barite
and fluorite. Under the influence of hydrothermal fluids, the lake water
would be heated to generate steam and then upwelled (Jiao et al., 2020).
Meanwhile, the host rocks reacted with hydrothermal fluids would
produce a large number of metallic ions (Kelley et al., 2001). The up­
welling could bring metallic ions to the photic zone, which would feed
primary producers (algae, bacteria, etc.) and increased bioproductivity
in the lake surface. Furthermore, H2S, SO2, HCl , HF and other toxic
gases produced by hydrothermal fluids may contribute to the formation
of extremely oxygen-deficient conditions in the bottom water, which is
favourable for the organic matter preservation (Zhang et al., 2020). In
addition, volcanic and hydrothermal activity could release thermome­
tamorphic or mantle-derived CO2 and thermogenic CH4 to promote
hydrocarbon generation and accumulation (Procesi et al., 2019).
Based on the above analysis, high bioproductivity in the lake surface
and good preservation conditions (anoxic and saline water) in the bot­
tom water column are present in the lake during volcanic and hydro­
thermal activity, which is favourable for the organic matter (OM)
enrichment. However, only low to moderate TOC contents are present in
the Unit I and upper part of Unit II1 (with volcanic and/or hydrothermal
activity; Fig. 8), which is controversial to the hypothesis (relatively high
TOC contents). The three main controlling factors for OM enrichment in
lacustrine basins are input, preservation and dilution of OM (Bohacs
et al., 2000). The input of OM is closely associated with bioproductivity,
whereas preservation is primarily related to bottom water column
conditions (e.g. redox; Katz, 2005). As relatively high bioproductivity
and good preservation conditions are present during deposition of the
Unit I and II1 (with volcanic and/or hydrothermal activity), the dilution
of OM is probably the main cause of low to moderate TOC in these units.
The dolostone in the Lucaogou Formation are considered as primary
B. Liu et al.
Fig. 8. Concentrations and concentration ratios of elements of the samples. Total organic carbon (TOC) and hydrogen index (HI) data is from Liu et al.
(2017, 2018a).
Fig. 9. Cross-plots of (a) pristane/phytane (Pr/Ph) and U/Th ratios; (b) gammacerane index (GI ¼ gammacerane/αβ C30 hopane) and Sr/Ba ratios. The values of Pr/
Ph and GI are from Liu et al. (2017).
lacustrine deposits derived from mantle-originated hydrothermal fluids,
as evidenced by REE and Sr–O isotopes (Liu et al., 2012). A negative
correlation is observed between TOC and MgO in all samples (r ¼ 0.64),
which may indicate an effect of dilution by dolomite. This conclusion is
further supported by the negative correlation between TOC and total
carbonate mineral content (r ¼ 0.63) in the Lucaogou fine-grained
sediments, as indicated in Jiao et al. (2020). An alternative explana­
tion for the low to moderate TOC contents in Unit I and Unit II1 is the
oxidation of OM during precipitation (Brazelton et al., 2006). This
explanation is corresponding to the relatively low HI values in these
units, as the oxidized aquatic OM is generally hydrogen-poor (Dow,
1977).
5.2. Provenance and tectonic setting
5.2.1. Chemical weathering
During the chemical weathering process, the alkali metal elements
8
Marine and Petroleum Geology 120 (2020) 104569
(e.g. Na, Ca and K) tend to be lost, whereas elements including Al and Ti
likely to be enriched in weathered products (Fedo et al., 1995). There­
fore, the relative proportions of these two kinds of elements could reveal
the degree of chemical weathering, such as the chemical index of
alteration (CIA) values (Nesbitt and Young, 1982). The CIA values in the
P2l2 SLORS vary between 27 and 46, with an average of 34 (Fig. 9),
reflecting a weak degree of chemical weathering. In contrast, the P2l2
SLORS from the Shitoumei Salient in Santanghu Basin reveals low to
moderate CIA values, which ranges from 41 to 60 (avg. 50, Fig. 10; data
from Tao et al., 2017). The relatively high CIA values in the P2l2 SLORS
from Tao et al. (2017) are probably because the Shitoumei Salient is
closer to the basin boundary fault (Fig. 1b).
5.2.2. Provenance
Immobile elements (La, Th, Co, Sc, Cr and Ni) concentrations and/or
their ratios have been widely applied to determine the provenance of
fine-grained sediments (e.g. Wani and Mondal, 2011; Moradi et al.,
B. Liu et al.
2016; Song et al., 2017, 2018). This is because siliceous rocks commonly
contain relatively high concentrations of La and Th, whereas basic rocks
generally show relatively high concentrations of Co, Sc, Cr and Ni.
Therefore, high ratios of La, Th to Co, Sc, Cr, Ni probably indicate a
silicic parent rock, whereas low ratios generally reveal a derivation from
basic sources (Cullers and Berendsen, 1998). The P2l2 SLORS reveal low
to moderate Th/Sc (0.05–2.15) and La/Sc ratios (0.50–6.02), and
moderate to high Co/Th ratios (0.67–22.07; Fig. 11), suggesting that
they are mainly derived from intermediate volcanic rocks, probably
mixed with small proportions of basic volcanic rocks. In addition, low
Zr/Sc ratios in the P2l2 SLORS indicate that they have not experienced
sediment recycling (zircon addition), as further supported by the results
from Tao et al. (2017). Intermediate to basic volcanic rocks were
developed in the vicinity of Santanghu Basin during the Late Carbonif­
erous (Xia et al., 2004). Therefore, the weathering products of these
volcanic rocks could provide sufficient sources during deposition of the
P2l2 in Santanghu Basin.
5.2.3. Tectonic setting
The element concentrations and/or ratios of fine-grained sediments
are diverse in different tectonic settings (arc, continental rift and colli­
sion; Armstrong-Altrin and Verma, 2005; Li et al., 2019). In this study,
the cross-plots of lg(K2O þ Na2O)–SiO2, Ti/Zr–La/Sc, and La/Y–Sc/Cr
(Fig. 12a–c), and the ternary diagrams of Th–Co–Zr/10, Th-Sc-Zr/10 and
La–Th-Sc (Fig. 12d–f) are integrated to distinguish the tectonic setting of
parent rocks for P2l2 SLORS. Nearly all the P2l2 SLORS (including the
samples from Tao et al., 2017) plot into the areas characterized by
continental island arc setting (Fig. 12). There are two different views
about the Late Carboniferous tectonic setting of Santanghu area, one is a
subduction setting (Xiao et al., 2008) and the other is a post-collisional
extension setting (Su et al., 2007). Based on the present results, we
consider that the intermediate-basic volcanic rocks from Late Carbon­
iferous in Santanghu area are probably formed in a subduction setting.
However, further work is needed to reveal the geochemistry and
geochronology of Late Carboniferous intermediate and basic volcanic
rocks in northwest China.
5.3. Shale oil potential and implications for regional hydrocarbon
exploration
Multiple prerequisites are needed for a successful shale oil play,
include appropriate thickness (>20 m) and burial depth (<5000 m),
Fig. 10. Ternary diagram based on Al2O3, K2O, CaO* and Na2O of the samples.
9
Marine and Petroleum Geology 120 (2020) 104569
moderate to high TOC contents (>2.0%), predominantly type I, II or IIS
kerogen, favourable thermal maturity (>0.85% Rr), and the occurrence
of low proportions of ductile minerals for the SLORS (e.g. Charpentier
and Cook, 2011; Jarvie, 2012; Andrews, 2013).
The P2l2 in Santanghu Basin is mainly composed of fine-grained
lacustrine mixed carbonate- and volcanic-clastic deposits, such as
mudstone, carbonate mudstone, tuffaceous mudstone and carbonate
rocks (Fig. 2). Coarse-grained sediments are only present in the
boundary of the basin (Liu et al., 2015). The thickness of P2l2 generally
varies between 40 and 120 m on the slope of the basin, and reaches 250
m thick in the center (Liu et al., 2018a). Moreover, the burial depth of
P2l2 is generally less than 5000 m.
The P2l2 SLORS contains relatively high TOC contents, generally
exceeding 2.0%, especially in the Unit II2 and III (Fig. 8; Liu et al., 2017).
In addition, relatively high oil saturation index (OSI), extractable
organic matter and saturated/aromatic hydrocarbon ratios are also
observed in the Unit II2 and III (Liu et al., 2017). Type I and II kerogen is
predominant in the P2l2 SLORS shale, as suggested by relatively high HI
values (Fig. 8). The ranges of Tmax (425–455 � C) and Rr (0.47 %–0.61%),
accompanies by the presence of exsudatinite in the P2l2 SLORS (Liu
et al., 2018a), indicating that the studied samples have reached an early
oil-window maturity.
Pores and fractures with nano-to micro-meter size were observed in
the P2l2 SLORS by Ar-ion milled SEM analysis, including inter-grain
pores, inter-crystalline pores, dissolution pores, organic matter pores
and microfractures (Fig. 13). Among them, inter-grain pores and
microfractures are the most common, followed by inter-crystalline pores
and dissolution pores, whereas organic matter pores are rare. These
micropores/nanopores and microfractures could provide storage space
for hydrocarbons.
Inter-grain pores are generally observed between rigid grains, such
as quartz, feldspar and dolomite (Fig. 13a–d). The inter-grain pores are
scattered and display no preferential orientation. Most of the inter-grain
pores are triangular in shape, which are considered as the remaining
pore space between compacted and cemented rigid grains (Loucks et al.,
2012). These triangular inter-grain pores are widely observed in the Unit
II2 and Unit III, accompanied by low contents of clay minerals (ductile
grains; Fig. 2). This is probably because the ductile grains would be
compressed and block the pore space between rigid grains, which is not
favourable for the development of inter-grain pores. Inter-crystalline
pores mainly occur within pyrite framboids in samples (Fig. 13c). The
inter-crystalline pores are mainly observed in the Unit I and Unit II1,
because the framboidal pyrite is generally formed in anoxic conditions
(Wilkin et al., 1996).
Dissolution pores, in the shape of dot or elliptical, are observed
within calcite and quartz (Fig. 13d). The calcite dissolution pores are
probably developed by acidic fluid generated during decarboxylation of
kerogen (Schieber, 2010; Liu et al., 2020). In contrast, quartz grains
were probably dissolved by alkaline underground water during early
diagenesis, due to the occurrence of volcanic and hydrothermal activity
during P2l in Santanghu Basin (see section 5.1.3). Organic matter pores
are rarely found in samples (Fig. 13e), consistent with the early
oil-window maturity. The organic matter pores mainly developed in
inertinite with well-preserved structures (Liu et al., 2018a), probably
indicating a short-distance transport of terrigenous organic matter.
Because of the short-term variation of paleoenvironment, laminated
structure is commonly developed in the P2l2 SLORS (Liu et al., 2015).
The microfractures mainly develop along the laminae and between
different laminae (Fig. 13f), including the carbonate laminae, clay-rich
(OM-rich) laminae, and silt-rich laminae. The microfractures could be
generated due to the differences of mechanical properties in different
laminae (Liang et al., 2017). In comparison to the freshwater-brackish
lacustrine SLORS (e.g. Liu et al., 2019), the SLORS in Santanghu Basin
contains relatively high abundance of pores and fractures, probably
because of the unique paleoenvironment, provenance and tectonic
setting.
B. Liu et al.
Fig. 11. Cross-plots of (a) Th/Sc and Zr/Sc ratios; (b) Co/Th and La/Sc ratios (after McLennan, 1993; Wronkiewicz and Condie, 1987).
Fig. 12. Cross-plots of (a) lg(K2O þ Na2O) and SiO2; (b) Ti/Zr and La/Sc; (c) La/Y and Sc/Cr; and ternary diagrams of (d) Th, Co and Zr/10; (e) Th, Sc and Zr/10; (f)
La, Th and Sc (after Roser and Korsch, 1988; Bhatia and Crook, 1986).
Brittleness of shale is an important factor for the recoverability of
unconventional hydrocarbons (shale oil/gas; Hester and Harrison,
2015). Most of the P2l2 SLORS contains relatively high brittle minerals
(quartz, feldspar, carbonate and pyrite) contents, except some samples
from the Unit I and the upper part of Unit II1 (around 3590 m), in which
the ductile clay minerals (mostly smectite) content up to 59.5% (Fig. 2).
The enrichment of brittle minerals (e.g. quartz, dolomite, pyrite) is
partly associated with hydrothermal activity.
Based on the above analysis, the SLORS in the P2l2 of Santanghu
Basin is characterized by high hydrocarbon generation potential,
abundant hydrocarbon storage space and high brittle minerals contents,
which reveals a significant shale oil exploration and exploitation po­
tential. However, due to the relatively low maturity of P2l2 SLORS in the
studied area, further shale oil exploration should be focused on the areas
where peak oil window maturity is reached. In addition, special atten­
tions should be paid on the upper part (equivalent to the Unit II2 and
Unit III) of P2l2 during artificial fracturing in Santanghu Basin, because
10
Marine and Petroleum Geology 120 (2020) 104569
of the relatively abundant micropores and microfractures, and high
brittle minerals contents.
6. Conclusions
Through XRD, XRF, ICP-MS and SEM analyses, the paleoenviron­
ment, provenance, tectonic setting and shale oil potential of salinized
lacustrine organic-rich shale (SLORS) in the second member of Middle
Permian Lucaogou Formation (P2l2) in the Santanghu Basin were
investigated. The results indicate that an evolution from anoxic, saline to
dysoxic-oxic, freshwater semi-deep to deep lake was prevailed during
deposition of the P2l2 SLORS. The evolution of paleoenvironment is
mainly caused by an increased freshwater inflow to the lake. Early in the
P2l2, volcanic and hydrothermal activity has promoted the flourishing of
microorganisms and therefore elevated the bioproductivity. The P2l2
SLORS is mainly originated from intermediate volcanic rocks, and mixed
with minor proportions of basic volcanic rocks. These parent rocks have
B. Liu et al.
Fig. 13. SEM images (Ar-ion milled) of micropores and microfractures in representative samples. (a) Inter-grain pores (red arrow) among quartz and feldspar. (b)
Inter-grain pores (red arrow) among quartz and dolomite. (c) Inter-crystalline pores (green arrow) among pyrites, and inter-grain pores (red arrow) among dolomite.
(d) Dissolved pores (green arrow) and inter-grain pores (red arrow). (e) Organic matter pores (red arrow). (f) Microfractures (red arrow). Q: quartz, F: feldspar, Py:
pyrite, Dol: dolomite, OM: organic matter, Kf: K-feldspar, Phos: phosphate mineral. (For interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)
experienced weak chemical weathering, and mainly derived from a
continental island arc setting. Variable kinds of micro-, nanopores and
microfractures are observed in the P2l2 SLORS, including inter-grain
pores, inter-crystalline pores, dissolution pores, organic matter pores
and microfractures. The pore-fracture system provides sufficient storage
space for hydrocarbons. The P2l2 SLORS is dominated by carbonate
minerals, quartz and feldspar, which all belong to brittle minerals and
favourable for artificial fracturing. The upper P2l2 SLORS hosts better
shale oil potential, because of the relatively high TOC, great abundance
of micropores and microfractures, and high brittle mineral contents. Our
data indicates that individual element geochemical parameters should
be used with caution, such as paleoredox proxy U/Th and paleosalinity
proxy Sr/Ba are not only influenced by paleoenvironment, but also by
volcanic and hydrothermal activity. This demonstrates the importance
of multi-proxy analysis during paleoenvironmental reconstruction.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Bo Liu: Resources, Writing - review & editing, Supervision, Project
administration, Funding acquisition. Yu Song: Conceptualization,
Methodology, Investigation, Data curation, Formal analysis, Writing -
original draft, Funding acquisition. Kai Zhu: Investigation. Peng Su:
Investigation. Xiang Ye: Investigation. Wanchun Zhao: Investigation.
Acknowledgement
We appreciate the constructive comments from Professor Reinhard F.
11
Marine and Petroleum Geology 120 (2020) 104569
Sachsenhofer of Montanuniversitaet Leoben (Austria) to significantly
improve the quality of this paper. This study is jointly supported by the
National Science Foundation of China (Grant No. 41902139,
41972156), Opening Fund of Key Laboratory of Continental Shale
Accumulation and Development (Northeast Petroleum University),
Ministry of Education (No. NEPUME-kfjj-001), and Opening Foundation
of Key Laboratory of Mineral Resources Evaluation in Northeast Asia,
Ministry of Natural Resources (DBY-KF-19-02).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.marpetgeo.2020.104569.
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