International Journal of Coal Geology 163 (2016) 52–71

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International Journal of Coal Geology

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

Applying sedimentary geochemical proxies for paleoenvironment

interpretation of organic-rich shale deposition in the Sichuan
Basin, China
Jianhua Zhao a, Zhijun Jin b,c,⁎, Zhenkui Jin a, Yikai Geng a, Xin Wen a, Caina Yan d
a
College of Geosciences, China University of Petroleum, Beijing 102249, China
b
State Key Laboratory of Shale Oil and Gas Enrichment Mechanisms and Effective Development, Beijing 100083, China
c
Petroleum Exploration and Production Research Institute, SINOPEC, Beijing 100083, China
d
School of Energy and Resources, China University of Geosciences, Beijing 100083, China

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

Article history: Depositional environment highly affects the geochemical feature of sediments recording the information of
Received 14 March 2016 paleoenvironment and its evolution. Geochemical data for Ordovician Wufeng Formation and Silurian Longmaxi
Received in revised form 18 June 2016 Formation black shale deposition in the Sichuan Basin are presented and applied as proxies for deciphering
Accepted 19 June 2016
paleoenvironment (detrital influx, redox conditions, paleoproductivity) and providing insight to
Available online 25 June 2016
paleoenvironmental conditions responsible for organic carbon accumulation. These data suggest that sili-
Keywords:
ceous shale in the Wufeng and Longmaxi Formations reveals high TOC content, whereas silty, argillaceous,
Paleoenvironment and limey shale display relatively low TOC contents. Major element and petrological evidences indicate that
Wufeng and Longmaxi Formations most of quartz in siliceous shales is biogenic origin (as shown by excess silica concentrations); therefore, Si is an
Sichuan Basin unreliable indicator of detrital influx. The similar distribution of detrital influx proxies (Ti/Al, Ce, Hf, La, Nb Th and
Geochemical proxies Zr) suggests a rather homogeneous coarse-grained detrital fraction supply. Redox proxies (Mo, Th/U, Ni/Co, V/Cr,
Biogenic silica and V/(V + Ni)) indicate that siliceous shales were deposited in a relatively dysoxic/anoxic environment, where-
Organic matter as the argillaceous, silty, and limey shales were deposited in a relatively oxic environment. Barium was solubi-
lized under reducing conditions and cannot be applied confidently as a paleoproductivity indicator in high-
TOC siliceous shales. Productivity proxies (Cu/Al, Ni/Al, excess Si) suggest that paleoproductivity was high during
siliceous shales deposition, and weak during argillaceous and limey shales deposition. Our data suggests that
high paleoproductivity and dysoxic/anoxic conditions controlled organic matter accumulation in Wufeng and
Longmaxi shales.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction sediments recording the information of paleoenvironment and its

The formation mechanism of organic-rich sediments is an unremit-
ting matter of controversy since the comparative study used between
the modern and ancient sedimentary environments (Pompeckj, 1901).
Extensive research has highlighted whether the accumulation of or-
ganic matter is mainly controlled by the bottom-water oxygen levels
(Demaison and Moore, 1980; Arthur et al., 1998; Mort et al., 2007),
or by primary productivity (Pederson and Calvert, 1990; Caplan
and Bustin, 1998; Sageman et al., 2003; Gallego-Torres et al., 2007),
and their effect on associated inorganic geochemical variations
(Rimmer et al., 2004; Morford et al., 2005; Perkins et al., 2008;
Rowe et al., 2008; Tribovillard et al., 2008; Ross and Bustin, 2009).
Depositional environment highly affects the geochemical feature of
⁎ Corresponding author at: State Key Laboratory of Shale Oil and Gas Enrichment
Mechanisms and Effective Development, Beijing 100083, China.
E-mail address: jinzj.syky@sinopec.com (Z. Jin).
evolution (Ganeshram et al., 1999; Morford and Emerson, 1999;
Böning et al., 2004; Borchers et al., 2005). Geochemical indicators
complement paleoenvironmental interpretations based on lithologic
descriptions and petrography, and provide clues to decipher
paleoceanographic conditions during organic-rich shale deposition
(Rowe et al., 2008; Ross and Bustin, 2009).
Oxidation state and solubility of trace elements are significant influ-
ence by redox status of the depositional conditions (Ganeshram et al.,
1999; Morford and Emerson, 1999; Borchers et al., 2005; Tribovillard
et al., 2006). Some redox sensitive elements (Ni, Cu, Zn, Cd) are mostly
deposited as organometallic complexes. During organic matter decay,
these elements may be incorporated into pyrite under sulfate reducing
conditions (Warning and Brumsack, 2000; Brumsack, 2006; Tribovillard
et al., 2006). It is hard to distinguish the source of trace metals in
organic-rich sediments (biogenic origin, terrigenous origin and diage-
netic enrichment; Brumsack, 2006). Therefore, major element analysis
is required, providing information on background sedimentary and

http://dx.doi.org/10.1016/j.coal.2016.06.015
0166-5162/© 2016 Elsevier B.V. All rights reserved.
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71 53

defining trace element enrichment or excess trace element contents
(Ross and Bustin, 2009).
Drastic environment changes in the Yangtze Platform (Block)
(Fig. 1A) through the Ordovician–Silurian transition were coincident
with stepwise mass extinctions (Rong et al., 1996; Chen et al., 2004;
Yan et al., 2009a), oceanic anoxia (Chen et al., 2004, 2005a; Wang
et al., 2008; Yan et al., 2009b, 2010; Su et al., 2009; Rong et al.,
2010; Liu et al., 2013), global sea-level changes (Chen, 1984; Su
et al., 2007), and regional paleogeographic configurations (Chen
et al., 2004). During Late Ordovician to Early Silurian, the Wufeng
and Longmaxi Formations have been characterized by widespread
organic-rich shale and mudstone deposition (Su et al., 2009), being
important source rocks for conventional oil and gas and important
shale gas resource plays in the Sichuan Basin and its periphery
(Fig. 1A) (Dong et al., 2010; Zou et al., 2010; Guo and Zhang, 2014).
The depositional paleoenvironment of the Wufeng and Longmaxi
organic-rich shale in the Sichuan Basin has been studied extensively
based on lithologic descriptions and petrographic, geochemical (trace
elements) and biostratigraphic approaches (Fig. 1B) (Chen et al., 1987,
2000a, 2003, 2005b; Li et al., 2009; Liang et al., 2009; Wang et al.,

(A)

(B)

Fig. 1. (A) Early Silurian paleogeographic map with the distribution of lithofacies of the Yangtze area (after Chen et al., 2004); (B) paleogeographic map of the Sichuan Basin and the
neighboring areas during the Early Silurian (modified from Guo and Zhang, 2014), showing the sampling sites.
54 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71
2009; Mou et al., 2011; Huang et al., 2011; Zeng et al., 2011; Liang et al.,
2012; Zhang et al., 2012; Wang et al., 2014a; Ran et al., 2015; Yan et al.,
2015). But most of these studies have been carried out on samples
obtained from outcrop sections in the Sichuan Basin. Due to the signifi-
cant exploration and development potential of shale gas, some impor-
tant wells were drilled, providing an abundance of data to research
the subsurface Wufeng and Longmaxi shales.
In this study, we present major and trace element data, and total
organic carbon (TOC) of shale samples collected from two cores and
a section in Wufeng and Longmaxi Formations in Guanyinqiao,
Sichuan Basin (Fig. 1B). The purpose of this study is to discuss the use
of sedimentary geochemical proxies as indicators for deciphering
paleoenvironmental conditions (detrital influx, redox condition,
paleoproductivity) of organic-rich shale deposition during Late
Ordovician to Early Silurian interval in the Sichuan Basin.
2. Geological setting
During the Ordovician period, carbonate deposition dominated in
the Upper Yangtze Platform. From the Late Ordovician to Early Silurian,
the Caledonian movement reached the highest intensity, placing the
Upper Yangtze Block under compression and leading to the formation
of the Chuanzhong uplift in the northwestern part of the Yangtze
Block, Qianzhong uplift in the southern part of the Block and
Jiangnan-Xuefeng uplift in the southeastern part of the Upper Yangtze
Fig. 2. Stratum and lithofacies section of the Wufeng and Longmaxi Formations in the Sichuan Basin (after Su et al., 2007; Xu et al., 2011; Chen et al., 2015). See Fig. 1B for the section
location.
Block (Liang et al., 2009; Zeng et al., 2011) (Fig. 1B). Due to the com-
pression and development of several uplifts around the Sichuan Basin,
the marine area was reduced to the northeast, east and southeast Si-
chuan Basin with relative rise in sea-level (Su et al., 2007; Huang
et al., 2011). At the same time, relatively low energy and anoxic condi-
tions dominated in the southeast Sichuan Basin, which led to thick, or-
ganic rich shale deposition in this area (Wang et al., 2009; Zhao et al.,
2016a) (Fig. 1B). There were two large global transgressions in the
Late Ordovician and Early Silurian. The Wufeng and Longmaxi shale
was the sedimentary deposit resulting from two global transgressions
(Su et al., 2007). Influenced by tectonic movement and transgression,
a set of thin-layered siliceous shales was deposited during the Late Or-
dovician period (Chen et al., 2000b), These siliceous shales were widely
distributed, ranging from a few meters to tens of meters thickness and
containing abundant graptolites (Chen et al., 1987, 2000b, 2003,
2005b; Su et al., 2007). The top of the Wufeng Formation (Guanyinqiao
Member) was usually deposited as a thin shell-rich marl and limey
mudstone with a rapidly sea-level fall, which was attributed to the lat-
est Ordovician glaciation (Rong et al., 2002; Chen et al., 2004, 2006). The
Guanyinqiao Member is locally thicker along the uplifts, with average
thickness being commonly less than 1 m (Rong, 1979). During the
Early Silurian Longmaxi Formation period, tidal flat facies and lagoon fa-
cies were mainly developed on the margin of the uplifts and most of the
Sichuan Basin was characterized by a restricted shelf (Mou et al., 2011;
Guo and Zhang, 2014) (Fig. 1). The lower Longmaxi Formation is
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71 55

Fig. 3. Lithological columns and sampling depths of the studied profiles.

composed of graptolites-bearing black organic-rich shales (Fig. 2). The
Upper Member is composed of siltstone, silty mudstone and argilla-
ceous limestone. The whole Longmaxi Formation displays TOC decreas-
ing upwards and siltstone content increasing upward, which suggests a
decreasing water depth from bottom to top. The Longmaxi Formation is
mainly distributed in the southeast and east Sichuan Basin with
thickness ranging from 160 to 600 m. Due to Chuanzhong uplift, the
Longmaxi shale has been eroded in the center and is limited to outcrops
in the northwestern Sichuan Basin (Fig. 2).
3. Samples and methods
Samples from Wufeng and Longmaxi shales were collected from two
wells (JY2 and YZ1) in the Sichuan Basin and Guanyinqiao section in the
southeastern part of the Sichuan Basin (Fig. 1B). A total of 62 samples
were collected from both formations for sedimentary, petrological,
TOC, and geochemical analyses (Fig. 3).
TOC contents were determined by IR spectroscopy using a CS Mat
230, treating each sample by hydrochloric acid (1:9 HCl:water) at
60 ± 5 °C (140 ± 41 °F) to remove the carbonate minerals, at the
State Key Laboratory of Petroleum Resources and Prospecting, China
University of Petroleum (Beijing).
X-ray fluorescence spectrometer (XRF) was used to determine
major element concentrations with analytical uncertainty b 3%.
Inducted Coupled Plasma Mass Spectrometer (ICP-MS) was used to
determine trace element concentrations. For the ICP-MS analytical
procedure, 50 mg samples were handled using 1 ml HF and 0.5 ml
HNO3 solution digestion in a screw top PTFE-lined stainless steel

Table 1
Mineralogical analysis of the Wufeng and Longmaxi shales.

Average mineral composition (wt.%)

Lithology Average TOC content (wt.%) Quartz K-feldspar Plagioclase Clay Carbonate Dolomite Pyrite

Siliceous shale 4.04 56.1 1.2 4.8 28.3 5.1 2.3 3.1
Silty shale 1.62 39.1 2.3 9.1 40.3 3.5 1.0 2.4
Argillaceous shale 0.74 34.7 0.3 5.6 53.8 4.9 0.1 0.8
Limey shale 0.28 31.6 / 3.8 40.7 23.9 / /
56 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71

Table 2
Average concentrations of Al-normalization major and trace elements of Wufeng and Longmaxi shales.

Average shalea Siliceous shale n = 19 Silty shale n = 19 Limey shale n=4 Argillaceous shale n = 20

Oxide/element Abundance –/Al Abundance –/Al EF Abundance –/Al EF Abundance –/Al EF Abundance –/Al EF

TOC (wt.%) 0.20 0.03 4.04 0.57 19.16 1.62 0.13 4.23 0.28 0.02 0.77 0.74 0.05 1.58
Al2O3 (%) 16.7 1 8.81 1 – 13.77 1 – 11.77 1 – 16.55 1 –
SiO2 (%) 58.9 3.53 70.07 10.13 2.87 64.33 4.91 1.39 42.18 3.70 1.05 4.04 0.42 1.02
Fe2O3 (%) 2.8 0.17 3.24 0.37 2.17 5.02 0.37 2.15 4.54 0.39 2.32 0.62 0.03 2.05
CaO (%) 2.2 0.13 2.82 0.41 3.12 2.04 0.15 1.18 15.89 1.78 13.68 2.38 0.16 1.32
MgO (%) 2.6 0.16 1.46 0.18 1.14 2.22 0.16 1.03 1.79 0.16 0.98 0.22 0.01 0.94
K2O (%) 3.6 0.22 2.27 0.25 1.16 3.40 0.25 1.13 2.84 0.24 1.09 0.32 0.01 0.40
Na2O (%) 1.6 0.10 0.72 0.08 0.81 1.06 0.08 0.80 0.14 0.01 0.13 0.29 0.02 0.84
TiO2 (%) 0.78 0.05 0.46 0.05 1.02 0.63 0.05 0.93 0.50 0.04 0.85 0.05 0.003 1.09
P2O5 (%) 0.16 0.01 0.25 0.06 5.72 0.11 0.01 0.83 0.10 0.01 0.85 0.02 0.002 0.54
Ag ppm 0.07 0.008 0.60 0.14 18.06 0.33 0.05 6.56 0.07 0.01 1.35 0.40 0.05 6.13
Ba ppm 580 65.6 1254.95 302.42 4.61 2572.68 370.49 5.65 567.50 95.46 1.46 1482.85 174.71 2.66
Be ppm 3 0.34 2.49 0.57 1.69 3.16 0.45 1.32 2.24 0.36 1.06 3.46 0.40 1.17
Bi ppm 0.1 0.011 0.30 0.07 6.20 0.40 0.05 4.98 0.33 0.05 4.37 0.47 0.05 4.98
Cd ppm 0.8 0.09 1.98 0.49 5.48 0.50 0.07 0.79 0.56 0.10 1.10 0.43 0.05 0.56
Ce ppm 95 10.7 59.56 13.03 1.22 81.39 11.74 1.10 65.00 10.70 1.00 93.17 10.71 1.00
Co ppm 19 2.15 13.65 3.02 1.41 15.21 2.24 1.04 6.60 1.10 0.51 10.94 1.26 0.59
Cr ppm 90 10.2 66.68 16.02 1.57 79.74 11.17 1.10 70.08 11.57 1.13 90.58 10.37 1.02
Cs ppm 5.5 0.62 6.25 1.30 2.10 9.98 1.38 2.22 7.38 1.18 1.91 11.28 1.29 2.09
Cu ppm 45 5.1 66.07 15.95 3.13 41.02 5.96 1.17 27.58 4.63 0.91 42.68 4.93 0.97
Ga ppm 19 2.1 14.38 3.23 1.54 21.25 3.00 1.43 17.03 2.73 1.30 24.48 2.80 1.33
Ge ppm 1.6 0.18 1.40 0.34 1.91 1.56 0.22 1.24 1.10 0.18 0.98 1.67 0.19 1.07
Hf ppm 2.8 0.32 2.85 0.61 1.89 3.89 0.58 1.80 1.87 0.30 0.92 3.35 0.39 1.22
La ppm 40 4.5 33.02 7.25 1.61 44.06 6.34 1.41 37.40 6.06 1.35 49.36 5.68 1.26
Mo ppm 2.6 0.29 36.60 9.30 32.08 9.46 1.46 5.03 1.88 0.33 1.12 4.58 0.55 1.90
Nb ppm 18 2.0 13.84 2.95 1.48 17.55 2.56 1.28 11.67 1.88 0.94 18.61 2.15 1.08
Ni ppm 68 7.7 96.06 23.74 3.08 56.91 8.20 1.06 34.13 5.71 0.74 48.66 5.60 0.73
Pb ppm 20 2.3 24.36 5.41 2.35 28.39 4.13 1.80 19.08 3.11 1.35 25.41 2.96 1.28
Rb ppm 140 15.8 120.97 26.32 1.67 173.74 24.56 1.55 141.43 22.74 1.44 205.75 23.57 1.49
Ta ppm 2 0.23 0.83 0.17 0.73 1.12 0.15 0.67 1.06 0.18 0.76 1.31 0.15 0.66
Th ppm 12 1.4 11.63 2.51 1.79 17.07 2.43 1.74 12.62 2.01 1.43 19.31 2.21 1.58
Tl ppm 1.4 0.16 2.14 0.46 2.86 1.71 0.25 1.54 0.73 0.12 0.72 1.43 0.17 1.04
U ppm 3.7 0.42 15.83 3.62 8.63 6.90 1.02 2.42 2.52 0.40 0.96 4.94 0.58 1.37
V ppm 130 14.7 300.79 72.67 4.94 140.89 20.21 1.37 95.38 15.31 1.04 148.40 17.01 1.16
Y ppm 41 4.6 26.45 6.20 1.35 27.15 3.97 0.86 24.68 4.16 0.90 27.36 3.16 0.69
Zn ppm 95 10.7 173.82 43.45 4.06 124.62 17.71 1.66 104.20 18.74 1.75 120.89 13.90 1.30
Zr ppm 160 18.1 125.19 27.45 1.52 158.16 23.74 1.31 69.40 11.09 0.61 137.44 16.00 0.88

Averages are also shown normalized to Al. EF: enrichment factors: EFelement = (element/Al)sample / (element/Al)average shale (Brumsack, 1989; Piper and Perkins, 2004).
a
Average shale composition from Wedepohl (1971) used to determine enrichment factors (EF).

bomb toasted in an oven at 200 °C for 48 h. The relative standard de- The average chemical composition of shales was calculated on the
viation of trace elements is b5%. Major element and trace element base of 277 samples from the literature, including the Paleozoic to Ceno-
analyses were completed at the Institute of Geochemistry, Chinese zoic shale samples from American, European, and Japanese study areas
Academy of Sciences. (Wedepohl, 1971). It is easy to see element concentrations deviation

Fig. 4. Enrichment factors (EF) of TOC and major elements in Wufeng and Longmaxi shales, in comparison to average shale (Wedepohl, 1971). A horizontal line represented
EFaverage shale = 1 to emphasize elements enrichment or depletion.
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71
Fig. 5. Ternary plot of these major elements showing the Wufeng and Longmaxi shales
enriched in SiO2 relatively to Al2O3 and CaO. Average shale is shown as box (after
Wedepohl, 1971).
form average shale (AS, Wedepohl, 1971) after Al-normalization; and
element enrichment factors (EFelement) were calculated as follows:
EFelement ¼ ðelement=AlÞsample =ðelement=AlÞaverage shale
whereas EFelement: element enrichment factors in sample, element: the
weighted concentrations of element, Al: the weighted concentrations
of element.
In addition, geochemical investigation were constrained by petro-
graphic studies, based on thin sections and X-ray Diffraction (XRD)
analysis. Thin polished sections were examined for petrographic
Fig. 6. Enrichment factors (EF) of trace elements in Wufeng and Longmaxi shales in comparison to AS (Wedepohl, 1971). A horizontal line represented EFaverage shale = 1 to emphasize
elements enrichment or depletion.
57
composition and texture under conventional transmitted polarized
light microscopy. The mineralogical composition of the bulk powder
samples (b 200 mesh) was determined by XRD at the State Key Labora-
tory of Petroleum Resources and Prospecting, China University of Petro-
leum (Beijing).
4. Results
4.1. Lithotypes and total organic contents
Thin sections and X-ray diffractograms observations were used to
identify four dominant shale lithotypes: siliceous, silty, argillaceous,
and limey shales. For Wufeng and Lower Longmaxi shales, the
mean TOC values are 2.28% (range: 0.30–4.23%) in JY2 samples and
2.77% (range: 0.18–5.79%) in YZ1 samples, respectively; the mean
TOC value for Guanyinqiao samples is 1.34% (range: 0.13–6.11%).
The siliceous shale has the highest TOC in all lithotypes, with mean
TOC value 4.04% (range: 1.44–6.11%). The silty shale averages
1.62% (range: 0.40–2.48%), the argillaceous shale 0.74% (range:
0.18–2.49%) and the limey shale exhibits a mean of 0.28% (range:
0.13–0.44%) (Table 1). Organic carbon in siliceous, silty and argillaceous
shales are enriched with enrichment factors in order of: limey shale
(0.77) b argillaceous shale (1.58) b silty shale (4.23) b siliceous shale
(19.16) (Table 2, Fig. 4).
4.2. Major elements
The ternary plot of major elements (SiO2, Al2O3, CaO) shows that the
ð1Þ Wufeng and Longmaxi shales are enriched in SiO2 relative to Al2O3 and
CaO (Fig. 5). High silica concentrations occur in Wufeng and Longmaxi
shales obtained from cores YZ1 (avg. SiO2 = 69.66%) and JY2 (avg.
SiO2 = 66.13%), and the Guanyinqiao section (avg. SiO2 = 56.72%).
The average silica content of the siliceous shale is 77.07% (range:
54.84–81.99%), and of the silty shale 64.33% (range: 57.30–77.80%);
these are both being higher than AS (Wedepohl, 1971). Silica concentra-
tion of the argillaceous shale averages 58.60% (range: 51.30–68.19%),
58 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71

Table 3
Major oxides, TOC contents and elements ratios of the Wufeng and Longmaxi shales.

Major oxides (%)

Sample Lithology TOC (wt.%) SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O TiO2 P2O5 MnO Excess Si (%) Ti/Al K/Al

G01 Siliceous shale 5.70 54.84 8.42 3.42 10.34 1.91 2.13 0.47 0.40 0.11 0.06 11.73 0.05 0.40
G02 Siliceous shale 6.11 63.07 9.66 4.77 3.08 1.84 2.53 0.66 0.60 0.10 0.03 13.53 0.07 0.41
G03 Siliceous shale 5.64 64.48 11.09 4.16 2.08 1.85 2.72 1.01 0.58 0.12 0.02 11.83 0.06 0.38
G04 Siliceous shale 3.99 61.61 11.45 4.55 4.00 2.15 2.92 0.75 0.55 0.09 0.03 9.90 0.05 0.40
G05 Siliceous shale 3.63 65.97 10.09 3.80 3.46 2.10 2.61 0.58 0.45 0.09 0.03 14.17 0.05 0.41
G06 Siliceous shale 2.22 63.71 12.38 4.30 3.54 2.10 3.17 0.60 0.58 0.09 0.03 9.34 0.05 0.40
G07 Siliceous shale 1.44 73.81 10.72 3.35 0.35 1.29 2.97 1.10 0.62 0.11 0.01 16.79 0.07 0.43
G08 Silty shale 1.02 59.89 13.64 4.87 4.56 2.73 3.12 1.27 0.67 0.09 0.05 5.49 0.06 0.36
G09 Silty shale 0.74 62.69 14.96 6.19 0.43 2.48 3.86 0.58 0.70 0.09 0.01 4.63 0.05 0.40
G10 Silty shale 0.46 61.95 16.83 5.89 0.57 2.55 3.72 0.64 0.67 0.08 0.01 1.19 0.05 0.35
G11 Silty shale 0.42 62.62 15.21 5.59 1.59 2.34 3.73 0.61 0.66 0.07 0.02 4.18 0.05 0.38
G12 Argillaceous shale 0.40 57.14 16.59 5.84 3.46 2.49 3.56 0.72 0.72 0.08 0.02 – 0.05 0.34
G13 Argillaceous shale 0.55 58.64 18.71 6.56 0.44 2.71 4.10 0.51 0.75 0.08 0.01 – 0.05 0.34
G14 Silty shale 0.40 59.21 15.90 5.95 2.71 2.41 3.84 0.62 0.72 0.08 0.02 1.45 0.05 0.38
G15 Silty shale 0.50 57.30 16.12 6.32 3.29 2.54 3.84 0.60 0.70 0.08 0.02 0.20 0.05 0.37
G16 Argillaceous shale 0.45 57.65 17.39 6.52 2.45 2.69 3.97 0.55 0.69 0.10 0.02 – 0.05 0.36
G17 Argillaceous shale 0.49 57.79 19.35 6.72 0.52 2.85 4.03 0.51 0.73 0.09 0.01 – 0.04 0.33
G18 Argillaceous shale 0.48 57.16 16.91 6.19 3.16 2.57 3.88 0.52 0.72 0.08 0.02 – 0.05 0.36
G19 Argillaceous shale 0.37 57.08 19.53 6.44 0.55 2.70 4.43 0.28 0.76 0.07 0.02 – 0.04 0.36
G20 Argillaceous shale 0.39 55.66 16.68 6.01 4.02 2.40 4.15 0.36 0.70 0.09 0.02 – 0.05 0.39
G21 Argillaceous shale 0.42 59.75 17.22 6.28 0.68 2.39 4.22 0.15 0.75 0.08 0.01 – 0.05 0.38
G22 Argillaceous shale 0.55 51.60 15.39 5.47 7.42 2.21 3.76 0.24 0.65 0.09 0.03 – 0.05 0.38
G23 Limey shale 0.44 48.44 13.46 5.33 10.52 1.97 3.28 0.22 0.60 0.10 0.04 0.44 0.05 0.38
G24 Argillaceous shale 0.33 49.77 14.53 5.46 8.84 2.13 3.58 0.27 0.63 0.09 0.03 – 0.05 0.39
G25 Limey shale 0.22 45.44 13.52 4.96 12.38 2.01 3.29 0.05 0.57 0.11 0.03 – 0.05 0.38
G26 Limey shale 0.33 46.61 13.69 5.03 11.32 2.01 3.32 0.12 0.58 0.10 0.03 – 0.05 0.38
G27 Limey shale 0.13 28.25 6.39 2.84 29.33 1.18 1.47 0.16 0.27 0.07 0.04 2.66 0.05 0.36
G28 Argillaceous shale 0.48 51.52 14.82 5.72 7.88 2.19 3.48 0.41 0.66 0.12 0.03 – 0.05 0.37
G29 Argillaceous shale 0.51 51.30 15.03 5.74 7.62 2.20 3.61 0.30 0.67 0.11 0.03 – 0.05 0.38
J01 Argillaceous shale 0.30 68.19 14.54 3.41 1.20 1.99 3.68 0.80 0.74 0.07 0.02 7.88 0.06 0.40
J02 Siliceous shale 4.14 64.66 11.56 5.62 1.77 1.35 2.89 0.68 0.92 0.10 0.02 11.14 0.09 0.39
J03 Siliceous shale 4.23 72.61 8.53 2.37 2.45 1.06 2.20 0.85 0.44 0.10 0.02 19.85 0.06 0.40
J04 Siliceous shale 3.87 69.49 9.53 3.33 3.17 1.37 2.64 0.76 0.50 0.08 0.02 16.74 0.06 0.43
J05 Siliceous shale 3.35 68.55 9.62 3.14 3.92 1.21 2.65 0.97 0.53 0.08 0.02 16.15 0.06 0.43
J06 Siliceous shale 3.81 68.68 10.51 4.20 1.91 1.48 2.93 0.64 0.49 0.08 0.02 14.74 0.05 0.44
J07 Silty shale 2.46 64.55 12.36 5.30 2.67 1.82 3.19 1.09 0.66 0.09 0.03 9.77 0.06 0.40
J08 Silty shale 2.13 68.25 11.28 5.08 2.08 1.62 2.94 0.95 0.57 0.09 0.02 13.28 0.06 0.41
J09 Silty shale 1.73 63.51 12.38 6.85 2.87 1.98 3.11 1.05 0.62 0.10 0.03 9.26 0.06 0.39
J10 Silty shale 1.84 64.28 14.24 4.96 2.06 2.16 3.54 0.78 0.57 0.09 0.03 6.56 0.05 0.39
J11 Silty shale 1.55 70.85 12.07 3.38 1.81 1.79 3.00 0.72 0.45 0.07 0.02 13.20 0.04 0.39
J12 Argillaceous shale 0.52 57.52 20.38 6.54 0.19 2.69 5.28 0.65 0.79 0.07 0.03 – 0.04 0.41
J13 Argillaceous shale 1.46 61.84 17.42 5.76 0.22 2.48 4.37 0.76 0.65 0.07 0.03 0.17 0.04 0.39
J14 Argillaceous shale 0.54 62.86 16.71 6.26 0.35 2.56 4.17 0.74 0.67 0.07 0.04 1.82 0.05 0.39
Y01 Argillaceous shale 0.18 65.11 16.70 3.90 0.54 2.83 4.01 1.10 0.67 0.05 0.03 2.89 0.05 0.38
Y02 Siliceous shale 3.10 81.37 6.71 2.12 0.24 1.08 1.51 0.59 0.31 0.01 0.01 26.93 0.05 0.35
Y03 Siliceous shale 4.26 77.86 8.03 1.94 0.08 1.22 1.90 0.74 0.36 0.02 0.01 23.11 0.05 0.37
Y04 Siliceous shale 2.96 81.99 2.34 1.01 4.25 0.93 0.49 0.15 0.11 0.07 0.05 34.40 0.05 0.32
Y05 Siliceous shale 5.40 75.69 3.40 1.28 3.32 1.23 0.79 0.23 0.16 2.92 0.02 29.72 0.05 0.37
Y06 Siliceous shale 5.79 81.18 4.01 1.61 1.35 0.65 1.05 0.40 0.19 0.17 0.01 31.28 0.05 0.41
Y07 Siliceous shale 5.14 72.16 7.80 3.22 1.85 1.31 2.11 0.64 0.35 0.23 0.02 20.84 0.05 0.42
Y08 Silty shale 2.26 77.80 6.97 2.46 1.30 0.98 1.98 0.98 0.39 0.19 0.01 24.84 0.06 0.45
Y09 Siliceous shale 1.90 69.69 11.60 3.35 2.37 1.64 3.01 1.78 0.62 0.11 0.03 13.43 0.06 0.41
Y10 Argillaceous shale 2.12 63.37 12.60 6.03 2.06 2.04 3.28 1.34 0.60 0.13 0.03 8.83 0.05 0.41
Y11 Silty shale 2.28 63.76 14.05 4.64 2.41 2.46 3.39 1.50 0.66 0.15 0.04 6.62 0.05 0.38
Y12 Silty shale 1.69 66.52 12.58 3.96 2.90 2.09 3.09 1.51 0.62 0.12 0.04 10.34 0.06 0.39
Y13 Silty shale 1.98 63.76 13.85 4.71 2.53 2.39 3.42 1.43 0.63 0.13 0.03 6.95 0.05 0.39
Y14 Silty shale 2.38 63.81 15.35 4.63 0.61 2.54 3.90 1.54 0.74 0.13 0.03 4.50 0.05 0.40
Y15 Silty shale 2.12 62.26 15.28 4.99 1.95 2.39 3.55 1.57 0.65 0.15 0.03 3.90 0.05 0.36
Y16 Silty shale 2.30 64.80 14.36 4.55 1.34 2.37 3.73 1.46 0.67 0.12 0.03 6.60 0.05 0.41
Y17 Argillaceous shale 2.49 63.26 15.14 5.03 1.01 2.71 3.59 1.14 0.61 0.13 0.04 4.60 0.05 0.37
Y18 Silty shale 2.48 64.46 14.18 5.00 1.11 2.52 3.70 1.32 0.66 0.11 0.03 6.73 0.05 0.41
Y19 Argillaceous shale 1.83 64.70 15.46 4.96 0.39 2.50 3.99 1.35 0.59 0.06 0.03 4.74 0.04 0.40

which is close to AS composition (Wedepohl, 1971). Limey shale ap-
pears to be enriched in CaO more than other lithotypes; it averages
15.89% (range: 10.52–29.33%), with an enrichment factor of 13.68
(Table 2).
Potassium and Ti are not significantly enriched in any of the samples
(Fig. 4). Titanium is stable during diagenetic process with EFs b 1.02
(Fig. 4). The similar distribution of K/Al and Ti/Al suggests a rather
homogenous detrital supply. All lithotypes contains low Na concen-
trations, which is related to the plagioclase content (Ross and
Bustin, 2008), possibly pointing that Wufeng and Longmaxi shales
contain relatively small amounts of plagioclase. Phosphorus concen-
trations are highly variable, with enrichment factors in order of: ar-
gillaceous shale (0.54) b silty shale (0.83) b limey shale
(0.85) b siliceous shale (5.72).
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71 59

Fig. 7. Cross-plot of excess-Si and Ti/Al of Wufeng and Longmaxi shales. The weak correlation implies that coarse-grain detrital sediment cannot completely account for the source of excess
silica in shales.

4.3. Trace elements
4.3.1. Large ion lithophile trace elements
Enrichment factors of Rb, Pb and Cs are relatively uniform in
all lithotypes (range: 1.28–2.35%), except Ba (range: 2.64–4.61%)
(Table 4, Fig. 6), which is formed from both detrital and biogenic origin
(Rutsch et al., 1995). The distributions of Rb and Cs are relatively uni-
form (Table 4). These elements are mainly terrigenous origin and their
contents appear varying with dilution of detrital and biogenic compo-
nent in the Wufeng and Longmaxi shales (Plank and Langmuir, 1998).
The enrichment factors of Cs, La and Be close to 1 (EFCe range:
1.00–1.21; EFLa range: 1.26–1.61; EFBe range: 1.06–1.69), implying

Fig. 8. (a) Backscattered electron image, detrital quartz silt with pore-filling authigenic quartz (sample J03); (b) SEM-CL image shows that quartz silt grain have strong luminescence; in
contrast, microcrystalline quartz is essentially non luminescent, suggesting a diagenetic origin. (c) Monochromatic CL-responses of quartz silt (red cross upper (a)); (d) monochromatic
CL-responses of microcrystalline quartz (red cross lower (a)), suggesting different origin for quartz silt.
60 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71
that background sedimentation during the Late Ordovician (Wufeng
Formation)–Early Silurian period (Longmaxi Formation) relatively sim-
ilar to that for AS (Wedepohl, 1971), and these elements (Ce, La and Be)
probably be adsorbed on the clay minerals (Ross and Bustin, 2009).
4.3.2. High field strength trace elements
High field strength elements (Zr, Hf, Nb, Ga, Ta and Th) are attribut-
ed to aluminosilicate component, but their concentrations do not corre-
late with Al2O3 in the shales of Wufeng and Longmaxi Formations.
Hafnium, Nb and Zr show enrichments in siliceous (EFHf = 1.89,
EFNb = 1.48, EFZr = 1.52) and silty shales (EFHf = 1.80, EFNb = 1.28,
EFZr = 1.31), and have concentrations close to this of AS in limey
(Wedepohl, 1971) (EFHf = 0.92, EFNb = 0.93, EFZr = 0.62) and argilla-
ceous shales (EFHf = 1.21, EFNb = 1.08, EFZr = 0.88) (Table 2, Fig. 6).
Tantalum concentrations are low in all lithotypes compared to AS
(Wedepohl, 1971). Gallium and Th concentrations are slightly enriched
in all lithotypes compared to AS (Wedepohl, 1971) (Table 2, Fig. 6). Ni–
Ta and Hf–Zr may be taken as element pairs, and they are not separated
during sedimentation and diagenesis (Plank and Langmuir, 1998).
Therefore, Nb and Hf can provide detrital influx information during de-
position (Taylor and McLennan, 1985).
4.3.3. Redox sensitive elements
Silver, Cd, Mo, Ni, Tl, U, V and Zn, have high EFs in siliceous shales,
whereas Ag, Mo, Tl, U and Zn are also enriched in silty shales. Silver
and, to a lesser extent, Mo and U are enriched in argillaceous shales
(Table 2, Fig. 6). Redox-sensitive elements concentrations are close to
those of AS in limey shales (Wedepohl, 1971). The Ag, Mo, Tl, U, and V
concentrations show the same trend in all four lithotypes, with EFs in
the order of: limey shale b argillaceous shale b silty shale b siliceous
shale. Siliceous shales show the highest levels enrichment of Mo
(EFMo = 32.08), which indicates anoxic conditions during deposition
(Dean et al., 1997).
5. Discussion
5.1. Excess silica concentrations
Si/Al ratios in siliceous and silty shales are significantly high. Excess
silica content is defined by SiO2 content in sample above AS background
and is calculated as follows:
h i
Siexcess ¼ Sisample − ðSi=AlÞbackground  Alsample
Fig. 9. Thin section of siliceous shale (sample J03). (a) Clotted peloidal texture with fossil fragments (yellow arrow); (b) silicified radiolarian with clear spurs.
whereas Siexcess: excess silica contents, Sisample: silica concentrations
in sample, Alsample: aluminum concentrations in sample, the value of
(Si/Al)background is 3.11 (Wedepohl, 1971), the average value for shales.
According to Eq. (2), up to 56% of the SiO2 in siliceous shales and up to
25% SiO2 in silty shales may not be present as aluminosilicate phase
(Table 3). Coarse-grain detrital sediment (quartz and feldspar grains)
reflected by Ti/Al ratios in certain cases, may possibly account for excess
SiO2 (Bertrand et al., 1996; Caplan and Bustin, 1998). However,
the weak correlation (R2 = 0.16) between excess-Si and Ti/Al in
this study suggests that a coarse-grained detrital sediment cannot
completely account for the source of excess silica in siliceous and silty
shales (Fig. 7). Cathodoluminescence is an efficient technique to distin-
guish provenance of quartz (Seyedolali et al., 1997). Low-luminescent
quartz under light microscopy, or non-luminescent quartz in scanning
mono-cathodoluminescence electron microscopy has commonly been
interpreted as being of low-temperature authigenic/diagenetic origin
(Zinkernagel, 1978; Matter and Ramseyer, 1985; Schieber et al., 2000).
Quartz grain in siliceous shale with uniform luminescence suggests a
detrital origin, but up to 50% of quartz in the form of microcrystalline ag-
gregation filling pores between clastic particles were essentially non-
luminescent under scanning mono-cathodoluminescence electron mi-
croscope; latter suggests an authigenic/diagenetic origin (Fig. 8). In ad-
dition, siliceous radiolaria assemblages were recognised in thin sections
(Fig. 9); these, suggest authigenic quartz is possibly originated from ra-
diolarians dissolution and re-crystallization. Biogenic silica is an impor-
tant component of marine mudstones and can provide material source
for authigenic quartz during burial diagenetic process (Peltonen et al.,
2009; Zhao et al., 2016b). Therefore, high excess silica concentrations
in siliceous and silty shales of the Wufeng and Longmaxi formations
may be from biogenic sources.
5.2. Detrital influx proxies
Aluminum, Ti, Si, Zr and Th contents have been widely used as de-
trital influx indicators (Murphy et al., 2000; Tribovillard et al., 2006).
Aluminum is the principal conservative for the detrital aluminosili-
cate component in fine-grain depositions (Arthur et al., 1985; Arthur
and Dean, 1991; Calvert and Pedersen, 2007). In this study, Al concen-
trations are generally higher in argillaceous shales (Table 3, Fig. 10), a
reflection of an increase in detrital clay influx. Titanium is often
contained in clays and heavy minerals like rutile, whereas Si is
contained both in detrital and biogenic components (Kidder and
ð2Þ Erwin, 2001). The Si/Al ratio has been utilized in previous studies as a
detrital influx proxy, which is a representation of the quartz to clay
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71 61

Table 4
Trace elements content and ratios of the Wufeng and Longmaxi shales.

Trace elements (ppm)

Sample
name Ag Ba Be Bi Cd Ce Co Cr Cs Cu Ga Ge Hf La Mo Nb Ni

G01 0.90 339.00 2.42 0.37 11.02 56.80 9.89 75.90 5.29 121.00 12.90 1.30 2.70 33.40 58.90 15.20 155.00
G02 0.89 618.00 3.19 0.40 3.70 74.80 18.20 82.40 7.24 102.00 16.30 1.30 3.94 40.40 93.30 13.00 146.00
G03 0.50 529.00 3.05 0.28 2.85 76.20 15.70 69.80 8.03 62.80 17.00 1.33 4.50 40.70 112.00 13.50 194.00
G04 0.18 550.00 2.91 0.37 1.79 67.00 17.90 67.00 9.31 59.30 16.60 1.23 3.05 38.80 41.70 13.30 99.00
G05 0.14 567.00 2.53 0.41 1.45 60.70 13.80 61.20 8.18 52.40 14.60 1.22 2.74 36.00 31.60 12.30 90.70
G06 0.12 558.00 2.50 0.49 0.83 66.40 16.30 69.30 10.30 47.80 16.90 1.27 2.93 38.50 15.20 13.30 61.80
G07 0.30 596.00 2.21 0.42 0.54 67.10 6.15 59.50 7.25 34.90 16.10 1.28 5.66 38.60 9.29 14.50 37.00
G08 0.09 522.00 2.85 0.20 0.46 75.50 14.10 72.20 9.61 32.50 19.10 1.37 5.40 42.60 7.40 14.90 50.80
G09 0.06 567.00 3.29 0.48 0.36 68.70 6.67 95.20 12.50 37.20 24.80 1.68 3.14 38.70 4.67 15.90 41.10
G10 0.03 590.00 3.22 0.32 0.35 84.20 6.90 91.10 12.10 37.10 24.90 1.67 3.41 45.30 3.30 16.90 39.60
G11 0.04 615.00 3.09 0.47 0.40 73.00 11.20 85.90 11.60 31.90 22.90 1.58 3.18 39.90 2.50 15.00 38.60
G12 0.09 642.00 3.02 0.47 0.53 84.10 7.90 86.70 9.29 35.60 22.50 1.52 3.48 43.00 3.79 15.80 42.50
G13 0.06 708.00 3.33 0.53 0.36 87.70 7.81 98.50 10.30 41.70 24.80 1.70 2.97 48.00 4.00 16.00 44.20
G14 0.11 676.00 3.05 0.46 0.52 78.80 10.10 87.80 10.40 36.90 22.80 1.55 3.15 42.50 3.47 15.40 44.50
G15 0.08 641.00 3.05 0.46 0.51 83.30 7.81 94.40 11.10 39.60 23.10 1.62 2.72 44.10 3.73 15.80 46.90
G16 0.04 668.00 3.05 0.49 0.51 85.60 8.44 92.90 10.80 38.70 24.40 1.66 2.61 43.90 3.40 15.70 47.50
G17 0.06 804.00 3.25 0.50 0.46 97.40 7.87 98.20 10.90 40.70 26.00 1.73 2.82 52.50 4.12 16.10 56.70
G18 0.06 698.00 3.12 0.60 0.53 86.10 8.52 89.30 11.00 41.70 23.40 1.61 2.82 45.20 4.07 15.80 47.20
G19 0.05 699.00 3.46 0.46 0.31 92.60 9.22 99.90 12.30 42.10 25.80 1.70 2.65 51.10 2.67 16.70 43.10
G20 0.10 653.00 3.26 0.35 0.60 82.90 6.13 95.00 11.00 39.50 24.30 1.57 2.53 45.60 3.04 15.40 42.80
G21 0.07 767.00 3.46 0.62 0.43 84.90 7.93 96.10 11.70 40.50 25.40 1.67 2.83 46.60 1.80 16.60 51.60
G22 0.06 639.00 2.90 0.57 0.64 78.60 7.21 86.30 9.79 38.90 21.60 1.39 2.48 43.00 3.74 14.50 45.50
G23 0.11 574.00 2.89 0.49 0.71 74.00 7.38 77.10 8.35 34.90 19.50 1.26 2.39 43.30 3.60 13.50 41.20
G24 0.08 615.00 2.80 0.44 0.46 77.90 7.45 81.60 9.35 30.60 21.40 1.37 2.43 42.30 3.02 14.10 43.30
G25 0.06 625.00 2.50 0.33 0.47 68.60 7.21 77.20 8.17 27.30 19.50 1.23 2.01 42.40 0.98 13.30 33.30
G26 0.08 651.00 2.29 0.41 0.52 75.20 7.25 79.70 8.98 28.00 20.00 1.29 2.14 42.30 1.32 13.50 37.60
G27 0.03 420.00 1.27 0.07 0.54 42.20 4.54 46.30 4.00 20.10 9.13 0.60 0.92 21.60 1.62 6.38 24.40
G28 0.22 669.00 2.72 0.54 0.55 79.50 6.95 85.10 9.40 32.00 20.90 1.35 2.37 40.90 2.40 14.50 41.10
G29 0.09 665.00 2.73 0.56 0.53 76.70 7.55 87.10 10.30 37.50 20.80 1.38 2.27 42.00 1.73 14.50 37.60
J01 0.35 2270.00 3.46 0.17 0.26 112.00 9.68 94.30 11.00 55.00 24.80 2.04 4.00 54.60 0.43 19.40 39.40
J02 3.05 2180.00 3.81 0.35 3.68 89.70 20.70 71.90 8.19 117.00 18.60 1.57 3.65 46.60 66.30 54.20 166.00
J03 0.55 1730.00 2.36 0.21 1.05 67.10 13.20 86.80 6.05 45.60 13.60 1.46 2.99 35.40 35.90 12.70 101.00
J04 0.49 2120.00 2.67 0.31 1.36 74.40 19.00 67.70 8.24 50.30 16.80 1.59 2.96 40.10 27.30 14.70 99.00
J05 0.49 1950.00 2.38 0.26 1.35 71.80 17.60 59.60 7.05 42.20 14.70 1.43 3.16 38.50 23.20 13.80 78.20
J06 0.55 2350.00 2.59 0.42 1.16 69.90 20.20 67.60 9.33 65.10 16.20 2.03 2.18 37.90 16.50 12.00 93.90
J07 0.54 2210.00 2.75 0.44 0.72 80.90 23.50 76.60 9.79 52.20 20.40 1.65 3.63 44.70 13.90 16.60 68.80
J08 0.49 2240.00 2.52 0.45 0.70 75.50 20.80 67.90 7.81 51.10 16.90 1.46 3.56 39.40 13.00 15.00 62.10
J09 0.49 2250.00 2.59 0.13 0.73 71.00 21.80 71.90 8.05 44.10 17.50 1.41 2.93 38.20 11.30 15.40 89.10
J10 0.46 11,700.00 3.25 0.54 0.57 89.20 18.60 83.80 11.60 47.80 23.00 1.63 2.76 48.40 12.70 15.80 66.40
J11 0.69 2260.00 3.17 0.14 0.51 105.00 8.06 77.50 8.86 26.70 23.80 1.63 4.69 56.00 11.20 43.40 45.60
J12 0.53 2910.00 5.08 0.47 0.22 131.00 24.00 115.00 15.00 37.00 32.40 1.95 3.55 62.20 2.04 17.70 52.50
J13 0.58 2020.00 4.20 0.49 0.36 90.30 17.00 102.00 13.00 36.90 27.00 1.77 3.02 49.00 7.70 19.50 63.70
J14 1.77 2020.00 3.34 0.17 0.47 94.40 14.50 93.60 12.10 29.60 24.00 1.67 3.08 49.70 4.58 14.40 45.70
Y01 0.62 2630.00 5.35 0.33 0.25 106.00 10.80 76.50 12.80 110.00 31.50 2.27 6.29 55.10 0.83 36.80 35.70
Y02 0.38 1120.00 1.42 0.29 0.22 42.80 7.40 78.60 3.86 117.00 11.10 1.43 1.62 25.90 1.54 7.94 48.70
Y03 0.76 1450.00 2.99 0.23 0.85 41.30 4.57 82.40 4.88 121.00 14.80 1.69 2.41 25.00 2.31 11.30 39.60
Y04 0.29 530.00 0.74 0.18 1.92 15.60 4.33 36.60 1.11 42.60 4.99 1.09 0.78 9.26 24.80 4.59 55.70
Y05 0.48 887.00 1.77 0.18 0.99 29.60 7.25 50.40 2.00 34.30 7.91 0.90 1.04 16.20 46.20 4.95 87.20
Y06 0.62 1330.00 2.22 0.12 1.19 33.80 8.58 44.60 2.34 31.40 8.86 1.06 1.19 18.60 45.60 6.39 116.00
Y07 0.47 2290.00 3.10 0.20 1.49 57.80 21.50 69.70 5.85 72.90 17.00 1.70 2.07 31.40 32.30 10.80 97.30
Y08 0.75 2660.00 3.25 0.18 0.44 103.00 20.10 69.00 6.29 56.80 21.30 1.75 6.55 53.80 20.40 23.10 60.00
Y09 0.32 2150.00 2.54 0.15 0.24 68.80 17.00 66.00 4.32 35.70 18.30 1.65 4.63 36.10 11.50 14.40 59.10
Y10 1.96 2840.00 3.44 0.58 0.42 78.60 16.70 70.50 9.61 43.70 18.40 1.41 3.83 41.50 13.90 14.70 36.20
Y11 0.33 2760.00 2.97 0.47 0.48 76.80 16.60 72.80 9.31 35.40 19.50 1.51 3.94 41.60 9.60 14.80 54.60
Y12 0.29 2700.00 3.41 0.38 0.37 74.70 14.80 71.40 7.74 28.30 18.30 1.36 4.12 40.50 7.39 14.30 50.20
Y13 0.34 3010.00 3.53 0.43 0.34 73.60 14.40 71.30 9.61 33.90 19.90 1.47 4.07 40.90 8.67 14.50 53.80
Y14 0.34 3130.00 4.59 0.47 0.41 84.50 17.10 84.70 10.40 35.10 20.40 1.67 4.69 45.50 10.60 16.30 64.50
Y15 0.41 3280.00 3.11 0.54 0.45 80.40 18.40 84.10 10.70 53.60 20.90 1.55 3.48 43.60 9.79 16.20 56.90
Y16 0.38 3390.00 3.12 0.54 0.79 84.30 18.80 77.60 10.50 55.00 20.90 1.50 4.72 45.50 11.80 15.50 74.60
Y17 0.35 3490.00 3.80 0.56 0.41 82.00 20.10 86.90 13.00 50.10 23.30 1.79 3.27 46.20 12.60 16.20 86.30
Y18 0.43 3680.00 3.27 0.52 0.36 84.10 19.20 79.80 11.60 44.10 23.30 1.57 3.84 46.00 14.40 18.70 73.10
Y19 0.83 3250.00 3.40 0.56 0.37 155.00 13.00 76.00 13.00 31.80 26.90 1.83 7.70 84.70 11.70 47.70 70.60

ratio (Murphy et al., 2000; Rimmer et al., 2004). Because biogenic silica
in siliceous and silty shales could possibly originate from radiolarians, it
could make silica or Si/Al ratios an unreliable indicator for detrital influx
(Schieber et al., 2000; Rimmer et al., 2004). The similar distribution of
Ti/Al for all samples in this study suggests a rather homogenous
coarse-grain detrital fraction supply in Wufeng and Longmaxi shales
(Fig. 10). The Al-normalized concentrations of detrital proxying trace
metals Ce, Hf, La, Nb, Th and Zr show the same trend with EFs in the
order of: limey shale b argillaceous shale b silty shale b siliceous shale
(Table 2, Fig. 6). These elements can be used to determine the source
of lithogenic portions in marine sediments (Brookins, 1988; Sugisaki
et al., 1982). Enrichment factors of these elements in siliceous and
silty shales (up to 1.89) are slightly higher than AS (Wedepohl, 1971)
suggesting a terrigenous origin.
62 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71

Table 4
Trace elements
Table content and ratios of the Wufeng and Longmaxi shales.
4 (continued)

Trace elements (ppm) Element ratios

Pb Rb Ta Th Tl U V Y Zn Zr Babio Cu/Al Ni/Al Th/U Ni/Co V/Cr V/(V + Ni)

26.90 116.00 0.78 10.83 2.68 23.91 875.00 39.60 437.00 137.00 338.97 27.15 34.78 0.45 15.67 11.53 0.85
34.90 124.00 0.96 12.75 4.08 23.13 461.00 41.50 221.00 179.00 617.96 19.95 28.55 0.55 8.02 5.59 0.76
35.20 132.00 1.00 14.56 4.06 48.14 556.00 36.50 329.00 171.00 528.96 10.69 33.03 0.30 12.36 7.97 0.74
27.50 148.00 1.00 13.59 2.51 16.88 219.00 29.80 131.00 123.00 549.95 9.78 16.33 0.80 5.53 3.27 0.69
27.80 135.00 0.90 12.21 2.67 11.98 252.00 27.90 165.00 111.00 566.96 9.81 16.97 1.02 6.57 4.12 0.74
25.50 159.00 1.07 13.69 2.24 6.80 170.00 23.50 108.00 113.00 557.95 7.29 9.43 2.01 3.79 2.45 0.73
26.80 133.00 1.08 14.65 1.24 6.19 122.00 23.20 95.40 225.00 595.96 6.15 6.52 2.37 6.02 2.05 0.77
20.70 156.00 1.13 17.87 1.39 6.33 122.00 28.30 130.00 211.00 521.95 4.50 7.03 2.83 3.60 1.69 0.71
20.80 152.00 1.30 14.33 1.17 4.10 133.00 21.60 138.00 116.00 566.94 4.70 5.19 3.49 6.16 1.40 0.76
19.40 155.00 1.34 17.89 1.10 4.30 131.00 25.50 143.00 138.00 589.93 4.16 4.44 4.16 5.74 1.44 0.77
19.30 159.00 1.28 17.03 1.06 3.59 116.00 21.40 129.00 121.00 614.94 3.96 4.79 4.74 3.45 1.35 0.75
21.70 181.00 1.36 18.71 1.07 4.26 127.00 24.30 123.00 133.00 641.93 4.05 4.84 4.39 5.38 1.46 0.75
23.30 189.00 1.38 19.85 1.25 4.01 142.00 26.30 129.00 112.00 707.93 4.21 4.46 4.95 5.66 1.44 0.76
21.30 197.00 1.30 17.37 1.10 3.66 129.00 23.50 115.00 119.00 675.94 4.38 5.29 4.74 4.41 1.47 0.74
21.80 205.00 1.33 18.23 1.10 3.60 133.00 23.50 115.00 104.00 640.94 4.64 5.50 5.07 6.01 1.41 0.74
22.50 206.00 1.28 18.25 1.18 3.59 136.00 23.50 122.00 100.00 667.93 4.20 5.16 5.09 5.63 1.46 0.74
24.20 184.00 1.37 20.95 1.28 4.23 140.00 28.60 127.00 105.00 803.92 3.97 5.54 4.95 7.20 1.43 0.71
24.00 206.00 1.31 18.86 1.19 4.04 138.00 24.10 110.00 111.00 697.93 4.66 5.27 4.67 5.54 1.55 0.75
21.60 214.00 1.35 22.07 1.20 3.76 136.00 26.20 141.00 103.00 698.92 4.07 4.17 5.87 4.67 1.36 0.76
19.70 210.00 1.40 19.47 1.05 3.70 131.00 24.30 146.00 93.40 652.93 4.47 4.85 5.26 6.98 1.38 0.75
23.80 217.00 1.39 19.80 1.16 3.72 146.00 26.30 133.00 108.00 766.93 4.44 5.66 5.32 6.51 1.52 0.74
22.30 181.00 1.20 17.37 1.07 3.92 133.00 22.40 111.00 89.90 638.94 4.77 5.58 4.43 6.31 1.54 0.75
26.40 163.00 1.13 16.03 0.96 3.57 120.00 26.10 110.00 88.80 573.95 4.90 5.78 4.49 5.58 1.56 0.74
22.00 175.00 1.17 15.67 0.93 3.35 132.00 24.30 113.00 90.20 614.94 3.98 5.63 4.67 5.81 1.62 0.75
14.20 158.00 1.25 13.56 0.81 2.57 96.80 28.00 100.00 73.00 624.95 3.81 4.65 5.28 4.62 1.25 0.74
24.00 167.00 1.14 14.46 0.80 2.62 113.00 26.20 98.80 79.60 650.95 3.86 5.19 5.52 5.19 1.42 0.75
11.70 77.70 0.72 6.41 0.35 1.33 51.70 18.40 108.00 36.20 419.97 5.94 7.21 4.81 5.37 1.12 0.68
21.90 176.00 1.20 18.09 0.94 3.63 116.00 23.60 100.00 90.50 668.94 4.08 5.24 4.99 5.91 1.36 0.74
21.20 175.00 1.19 17.71 0.98 3.44 115.00 25.40 104.00 88.70 664.94 4.71 4.73 5.15 4.98 1.32 0.75
31.50 239.00 1.60 21.91 1.70 3.29 105.00 26.20 114.00 167.00 2269.94 7.14 5.12 6.67 4.07 1.11 0.73
41.70 159.00 3.06 16.05 4.09 37.96 703.00 35.40 193.00 172.00 2179.95 19.12 27.12 0.42 8.02 9.78 0.81
20.00 126.00 0.80 13.28 2.43 25.10 279.00 31.90 163.00 126.00 1729.97 10.10 22.38 0.53 7.65 3.21 0.73
23.10 147.00 1.10 15.17 2.55 16.97 240.00 25.90 122.00 120.00 2119.96 9.97 19.63 0.89 5.21 3.55 0.71
27.10 144.00 1.00 13.73 2.64 15.31 208.00 23.80 120.00 125.00 1949.96 8.29 15.36 0.90 4.44 3.49 0.73
28.40 172.00 0.95 14.12 2.45 13.14 196.00 21.50 127.00 75.90 2349.96 11.70 16.87 1.07 4.65 2.90 0.68
36.90 187.00 1.49 17.52 2.25 8.47 163.00 26.90 119.00 139.00 2209.95 7.98 10.51 2.07 2.93 2.13 0.70
41.70 162.00 1.20 17.19 1.96 9.59 119.00 23.90 96.70 137.00 2239.96 8.56 10.40 1.79 2.99 1.75 0.66
50.10 175.00 1.02 16.51 2.08 6.91 147.00 22.80 148.00 109.00 2249.95 6.73 13.60 2.39 4.09 2.04 0.62
31.10 228.00 1.30 18.69 2.11 9.57 157.00 27.30 121.00 104.00 11,699.94 6.34 8.81 1.95 3.57 1.87 0.70
18.10 159.00 1.16 15.57 1.65 6.49 221.00 37.30 145.00 257.00 2259.95 4.18 7.14 2.40 5.66 2.85 0.83
38.60 301.00 1.61 25.21 1.96 4.91 188.00 33.20 98.80 130.00 2909.92 3.43 4.86 5.13 2.19 1.63 0.78
31.00 233.00 1.29 22.54 1.86 8.82 203.00 27.50 91.10 140.00 2019.93 4.00 6.91 2.55 3.75 1.99 0.76
21.50 226.00 1.14 18.82 1.51 6.26 189.00 26.70 118.00 112.00 2019.93 3.35 5.16 3.01 3.15 2.02 0.81
19.40 225.00 0.89 17.80 1.43 2.88 139.00 31.40 166.00 324.00 2629.93 12.44 4.04 6.18 3.31 1.82 0.80
20.00 84.80 0.35 8.56 0.52 2.56 121.00 15.50 147.00 77.60 1119.97 32.94 13.71 3.34 6.58 1.54 0.71
10.10 106.00 0.37 9.66 0.65 2.69 291.00 13.70 218.00 133.00 1449.97 28.46 9.31 3.59 8.67 3.53 0.88
7.71 31.70 0.19 2.98 0.58 5.26 171.00 13.60 139.00 47.10 529.99 34.33 44.89 0.57 12.86 4.67 0.75
12.00 52.70 0.24 4.98 0.87 10.50 198.00 15.20 88.10 51.50 886.99 19.04 48.40 0.47 12.03 3.93 0.69
16.80 65.30 0.18 5.43 1.04 17.10 305.00 24.80 170.00 61.60 1329.98 14.79 54.63 0.32 13.52 6.84 0.72
27.10 133.00 0.32 11.00 2.08 10.90 226.00 25.20 215.00 104.00 2289.97 17.66 23.57 1.01 4.53 3.24 0.70
33.50 162.00 0.48 17.90 1.82 9.87 149.00 39.80 127.00 308.00 2659.97 15.40 16.27 1.81 2.99 2.16 0.71
24.20 130.00 0.36 13.70 1.24 6.28 122.00 34.00 114.00 226.00 2149.95 5.81 9.63 2.18 3.48 1.85 0.67
39.90 162.00 1.01 16.50 2.12 7.38 96.90 25.70 91.80 145.00 2839.95 6.55 5.43 2.24 2.17 1.37 0.73
27.20 161.00 1.01 16.10 1.66 6.46 120.00 27.20 103.00 156.00 2759.94 4.76 7.34 2.49 3.29 1.65 0.69
23.00 148.00 0.94 15.90 1.58 5.43 120.00 27.00 102.00 160.00 2699.95 4.25 7.54 2.93 3.39 1.68 0.71
24.60 165.00 1.01 16.50 1.80 6.40 120.00 26.50 119.00 156.00 3009.94 4.62 7.34 2.58 3.74 1.68 0.69
30.70 176.00 1.01 17.70 1.93 7.96 126.00 27.60 118.00 190.00 3129.94 4.32 7.94 2.22 3.77 1.49 0.66
35.60 181.00 0.98 16.70 2.16 7.82 141.00 26.30 113.00 139.00 3279.94 6.63 7.04 2.14 3.09 1.68 0.71
35.10 180.00 0.99 17.80 2.27 11.00 173.00 30.60 164.00 183.00 3389.94 7.23 9.81 1.62 3.97 2.23 0.70
29.20 203.00 0.99 17.60 2.43 8.55 241.00 28.20 148.00 128.00 3489.94 6.25 10.77 2.06 4.29 2.77 0.74
28.60 193.00 1.04 17.50 2.26 9.58 157.00 28.90 122.00 158.00 3679.94 5.87 9.74 1.83 3.81 1.97 0.68
28.90 212.00 2.13 19.10 2.26 11.00 214.00 49.00 131.00 378.00 3249.94 3.89 8.63 1.74 5.43 2.82 0.75

5.3. Redox proxies
Modern reducing sediments with free H2S exhibit enrichment in
Mo, such as Black Sea sediments (2–40 ppm) and Saanich Inlet sedi-
ments (50–125 ppm) (Crusius et al., 1996). The Mo contents in AS
(2.6 ppm) (Wedepohl, 1971) and black shales from North America
(10 ppm) (Vine and Tourtelot, 1970) are relatively low, except in
some Pennsylvanian marine black shales (N1000 ppm) (Coveney and
Martin, 1983; Coveney and Glascock, 1989). Enrichment mechanism
of Mo remains controversial, but the Mo content determined in the
studied shale samples can provide insight to paleoredox conditions
(Bertine, 1972; Pilipchuk and Volkov, 1974; Francois, 1988; Calvert
and Pederson, 1993; Crusius et al., 1996; Helz et al., 1996). The Mo con-
tents of the siliceous shales range from 1.54 to 99.3 ppm (average of
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71 63

36.6 ppm), which is close to that of Black Sea reduced sediments, and
from 2.5 to 20.4 ppm with (average of 9.5 ppm) in silty shales, close
to black shales from North America (10 ppm) (Vine and Tourtelot,
1970), and from 0.43 to 13.9 ppm (average of 4.5 ppm) in argilla-
ceous shales and from 0.98 to 3.6 ppm (average of 1.9 ppm) in
limey shales, close to that of AS (Wedepohl, 1971). Uranium and
Mo have been used to investigate redox conditions and processes
in marine sediments (Fig. 11), using enrichment factors crossplot
to identify three patterns of U–Mo covariation (unrestricted marine
systems, strongly restricted basin and weakly restricted basin),
each of which is related to a different modern marine setting
(Algeo and Tribovillard, 2009). Most siliceous shale samples plot in
areas near the unrestricted marine anoxic to restricted marine
euxinic end, while most silty, argillaceous and limey shale samples
plot near the suboxic end (Fig. 11).
Trace element ratios (Th/U, Ni/Co, V/Cr, and V/(V + Ni)) can provide
information of paleoredox conditions (Hatch and Leventhal, 1992;
Jones and Manning, 1994; Rimmer et al., 2004). Thorium is usually
concentrated in clay sediments under oxic conditions (Adams and
Weaver, 1958; Wignall and Myers, 1988). Sediments will trap aque-
ous U under organic-rich reducing conditions (Kochenov et al.,
1977; Holland, 1984). Thus, low Th/U ratios are typical of anoxic
conditions with high authigenic U. Th/U b 2 has been widely used
as a anoxic sediments indicator (Wignall and Twitchett, 1996). Nick-
el and V are sequestered in organic matter under anoxic conditions
(Lewan and Maynard, 1982; Breit and Wanty, 1991). While redox con-
ditions do not influence Co and Cr concentrations, which are related to
detrital component (Ross and Bustin, 2006). Therefore, high Ni/Co, V/Cr,
and V/(V + Ni) values are considered to reflect anoxic conditions (Jones
and Manning, 1994). In Wufeng and Longmaxi shale samples, a very
consistent interpretation of paleoredox conditions using standards for
Th/U, Ni/Co and V/Cr (Fig. 10). However, V/(V + Ni) ratios of Wufeng
and Longmaxi shale samples range from 0.62 to 0.88 pointing to all in
anoxic conditions, whereas other proxies indicate oxic to dysoxic ones
(Fig. 10).
Crossplots of redox proxies is an integrated approach to investigate
redox conditions (Fig. 12). Most of siliceous shale samples are plotted
in the dysoxic and anoxic fields, while most of argillaceous, silty, and

(A)

Fig. 10. (A) Stratigraphic distribution of TOC, detrital influx proxies (Al, Ti/Al), redox proxies (Mo, Th/U, Ni/Co, V/Cr and V/(V + Ni)) and paleoproductivity proxies (Babio, Cu/Al, Ni/Al and
excess-Si) in Guanyinqiao section; (B) stratigraphic distribution of TOC, detrital influx proxies (Al, Ti/Al), redox proxies (Mo, Th/U, Ni/Co, V/Cr and V/(V + Ni)) and paleoproductivity
proxies (Babio, Cu/Al, Ni/Al and excess-Si) in core JY2; (C) stratigraphic distribution of TOC, detrital influx proxies (Al, Ti/Al), redox proxies (Mo, Th/U, Ni/Co, V/Cr and V/(V + Ni)) and
paleoproductivity proxies (Babio, Cu/Al, Ni/Al and excess-Si) in core YZ1.
64 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71

(B) Well JY2

(C) Well YZ1

Fig. 10 (continued).

limey shale samples are plotted in the oxic and dysoxic fields. All of 5.4. Paleoproductivity proxies
these facts suggest that the siliceous shale was deposited in a relatively
dysoxic/anoxic conditions, while the argillaceous, silty and limey shales Barium is considered as a paleoproductivity proxy since the biogenic
were deposited in a relatively oxic conditions. barite is connected with phytoplankton decay (Dymond et al., 1992;
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71
Fig. 11. Enrichment factors (EF) of Mo vs. U, showing that most siliceous shale samples plot in areas near the unrestricted marine anoxic to restricted marine euxinic end, while most silty,
argillaceous and limey shale samples plot near the suboxic end. Base figure modified from Algeo and Tribovillard (2009).
Francois et al., 1995; Monnin et al., 1999; Jeandel et al., 2000). Biogenic
Ba (Babio) has been proven as a indicator to estimate carbon export from
the photic zone in the water column and is considered to be a reliable
paleoproductivity proxy (Brumsack, 1989; Tribovillard et al., 1996;
McManus et al., 1998a, 1998b, 1999; Martinez-Ruiz et al., 2000;
Joachimski et al., 2002; Eagle et al., 2003; Averyt and Paytan, 2004;
Tribovillard et al., 2004; Riquier et al., 2005). Babio content is determined
using the formula:
Babio ¼ Batot −ðAltot Ba=Alalu Þ ¼ Batot −ðAltot  0:0075Þ
whereas Babio: the biogenic Ba content, Batot: the total Ba content,
Ba/Alalu: the Ba/Al ratios of aluminosilicate detritus in crustal rocks,
Altot: the total Al content. It assumes that all the Al in sediments is
form aluminosilicate. The Ba/Alalu ratios of aluminosilicate compo-
nent range from 0.005 to 0.01 in crustal rocks (Taylor, 1964) and
the value of 0.0075 is widely used to calculate Babio content
(Dymond et al., 1992). Ba tot and Babio concentrations are lower in
high TOC siliceous shale than in low TOC silty and argillaceous shales
in both cores studied and the Guanyinqiao section as well. However,
barite will dissolve in sulfate reducing conditions and Ba will mi-
grate to pore water, which may make Batot and Babio concentrations
an unreliable paleoproductivity indicator in organic-rich sediments
developed under this conditions (Van Os et al., 1991; Torres et al.,
1996; van Santvoort et al., 1996). Therefore, the low Batot and Babio
concentrations in high TOC siliceous shale do not necessarily sug-
gest a lower paleoproductivity than that in silty and argillaceous
shales.
Nickel and Cu are mostly deposited as organometallic complexes.
During organic matter decay, released Ni and Cu may be incorporated
into pyrite under sulfate reducing conditions (Fernex et al., 1992;
Algeo and Maynard, 2004; Piper and Perkins, 2004). Although the
sedimentary organic matter degraded after deposition, Ni and Cu
can point to its primary presence. Therefore, we hold that Ni and
Cu may be used as reliable productivity indicators. The Cu/Al and
Ni/Al ratios show the uniform trends, with the order of limey
65
shale b argillaceous shale b silty shale b siliceous shale in both well
cores and the Guanyinqiao section as well. In addition, excess silica
concentrations is a result of precipitating authigenic quartz form ra-
diolarians dissolution and re-crystallization, and its contents (excess
silica) may point to paleoproductivity (Schieber, 1996). Excess silica
contents show trends similar to Cu/Al and Ni/Al ratios (Fig. 10).
5.5. Paleoenvironment interpretation
ð3Þ 5.5.1. Paleoenvironmental conditions during siliceous shale deposition
Siliceous shale occurs in the Wufeng and lower Longmaxi Formation,
and is mainly enriched in SiO2 and organic matter, deposits in a dysoxic/
anoxic restricted shallow marine environment. High excess silica
(biogenic origin) and paleoproductivity proxies (Cu/Al, Ni/Al) indi-
cate high paleoproductivity, which is related to upwelling (Wang
and Zhang, 2011; Ran et al., 2015). During the Ordovician and Siluri-
an, the Yangtze block was located in low latitudes of the Northern
Hemisphere (Metcalfe, 2006), and its western part was open to the
ocean (Li et al., 2005). Coastal winds may have generated upwelling,
and volcanic eruptions could have generated volcanogenic upwell-
ing as well (Su et al., 2009). Aluminum contents are low in siliceous
shale, pointing to lower detrital clay influx. Alternatively, the lower
Al contents could be the result of sea-level rise during siliceous
shale deposition (Chen et al., 2004; Su et al., 2009). Redox proxies
(Mo, Th/U, Ni/Co, V/Cr, and V/(V + Ni)) suggest that dysoxic/anoxic
paleoenvironmental conditions were widespread during siliceous
shale deposition, especially in the Wufeng Formation and the lower
Longmaxi Formation. At end of the Ordovician, a rapid rise and inten-
sification of the oceanic chemocline resulted by rapid global warming
and melting of the Gondwanan ice sheet may lead to widespread ocean
anoxia (Zhang and Barnes, 2002). High paleoproductivity, relatively low
detrital influx and dysoxic/anoxic conditions controlled the accumula-
tion of organic matter during siliceous shale deposition (Fig. 13). The
strong correlations of TOC vs. Th/U (R2 = 0.75) and TOC vs. Mo
(R2 = 0.68) imply that the organic carbon accumulations mainly result-
ed from an anoxic water column (Fig. 13).
66 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71

(A) (B)

(C) (D)

(E) (F)

Fig. 12. Crossplots of paleoredox proxies. (a) Ni/Co vs. Th/U; (b) V/Cr vs. Ni/Co; (c) V/Cr vs. Th/U; (d) V/(V + Ni) vs. Ni/Co; (e) V/(V + Ni) vs. Th/U; (f) Mo vs. Ni/Co. Ranges for Th/U are
from Wignall and Twitchett (1996); ranges of redox proxies are from Jones and Manning (1994) and Hatch and Leventhal (1992).

Paleoenvironmental conditions show differences among the studied
cores and the Guanyinqiao section. The thickness of the siliceous
shale interval in core JY2 is 30 m, which is thicker than that in the
YZ1 core and the Guanyinqiao section (Fig. 14), suggesting deeper
water conditions at the JY2 site during siliceous shales deposition.
In the Ordovician–Silurian, site YZ1 was located close to the Yichang
submarine high, and the Guanyinqiao section close to the Qianzhong
uplift, while site JY2 was located at depositional center with relative-
ly deep water. However, higher SiO 2 concentrations and higher
paleoproductivity proxies (Cu/Al, Ni/Al) occur in siliceous shale sam-
ples from core YZ1, suggesting higher paleoproductivity during sili-
ceous shale deposition. The distributions of radiolarian show an
 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71
(A)
(C)
Fig. 13. Crossplots of TOC contents vs. (a) Th/U, (b) Mo, (c) Cu/Al, (d) Al2O3 of the samples in Wufeng and Longmaxi shales.
increase in the northward direction of the Upper Yangtze block dur-
ing late Ordovician (Ran et al., 2015). We consider that higher
paleoproductivity at site YZ1 may possibly be related to intensified
upwelling toward the northeast of the basin.
5.5.2. Paleoenvironmental conditions during silty shale deposition
After the deposition of siliceous shale, the oxygen concentration
gradually increased. Silty shale occurs in the mid of the lower Longmaxi
Formation, indicating sedimentation in an oxic, shallow marine en-
vironment. Silty shale includes low angle cross-laminations, indicat-
ing relatively strong hydrodynamic conditions during deposition
(Liang et al., 2012; Wang et al., 2014b; Zhao et al., 2016b). Low ex-
cess silica concentrations (biogenic origin) and paleoproductivity
proxies (Cu/Al, Ni/Al) being slightly higher than AS (Wedepohl,
1971), indicate moderate paleoproductivity. Redox proxies sug-
gested that dysoxic/oxic conditions were widespread during silty
shale deposition. The relative sea-level fall may have led to an increase
of oxygen concentration, which, in turn, resulted in the poor organic
matter retention.
According to redox proxies and detrital influx proxies, silty shales in
Guanyinqiao section show higher oxygen and Al2O3 concentrations re-
lated to the location of Guanyinqiao section close to Qianzhong uplift,
which resulted in higher detrital clay influx.
5.5.3. Paleoenvironmental conditions during argillaceous and limey shales
deposition
Argillaceous shale and limey shale occur in upper Longmaxi Forma-
tion, being characterized by sedimentation in an oxic shallow marine
67
(B)
(D)
environment. Detrital influx, mainly terrigenous clay, was likely
enhanced by a fall in sea-level (Wang et al., 2014c; Chen et al.,
2015) as indicated by high Al concentrations. Paleoproductivity
proxies indicated a weak primary productivity during argillaceous
shale deposition. Redox proxies suggest that oxic conditions were
widespread during argillaceous and limey shales deposition. The
weak paleoproductivity and the oxic conditions led to poor OM re-
tention in the sediments. Besides the influence of paleoproductivity
and redox conditions, the clay minerals content also affects OM ac-
cumulation in Longmaxi shales. Numerous studies have stressed
the importance of clay minerals for organic carbon preservation
(Kennedy et al., 2002; Ross and Bustin, 2009; Jia et al., 2013). How-
ever, a negative correlation is observed between Al 2O 3 and TOC
contents (R2 = 0.51) implying that clay minerals content is
not key factor for OM retention in Wufeng and Longmaxi shales
(Fig. 13d).
6. Conclusions
Based on TOC contents and sedimentary geochemical proxies for
paleoenvironmental reconstruction of the organic-rich shales of the
Wufeng and Longmaxi Formations from the Sichuan Basin, China, we
conclude the following:
(1) All shale lithotypes studied except limey shale are enriched in or-
ganic carbon in comparison to AS (as defined by Wedepohl,
1971). The highest mean TOC value is that of siliceous shale:
4.04% (range: 1.44–6.11%). The mean TOC value of silty shale is
68 J. Zhao et al. / International Journal of Coal Geology 163 (2016) 52–71
Fig. 14. Comparison of paleoenvironment conditions from the section to wells during Wufeng and Longmaxi shales deposition.
1.62% (range: 0.40–2.48%), of argillaceous shale 0.74% (range:
0.18–2.49%) and of limey shale 0.28% (range: 0.13–0.44%).
(2) Up to 50% of quartz in the form of microcrystalline aggregation
filling pores between clastic particles, is of authigenic/diagenetic
origin, possibly originated from radiolarians dissolution and re-
crystallization. This type of quartz could make silica and Si/Al ra-
tios unreliable indicators of detrital influx. The similar distribu-
tion of Ti/Al in studied samples suggests a rather homogeneous
detrital coarser-grained component supply for the Wufeng and
Longmaxi shales.
(3) Redox proxies indicate that the siliceous shale was deposited
in a relatively dysoxic/anoxic conditions, while the argilla-
ceous, silty, and limey shales were deposited under relatively
oxic conditions.
(4) Barite will dissolve in sulfate reducing conditions and Ba will mi-
grate to pore water. The low Batot and Babio concentrations in high
TOC siliceous shale is not suggest the lower paleoproductivity
than that in silty and argillaceous shales. Paleoproductivity
proxies (excess silica, Cu/Al, Ni/Al) show the same trends, with
order of: limey shale b argillaceous shale b silty shale b siliceous
shale.
(5) High paleoproductivity, lower detrital influx and dysoxic/an-
oxic conditions controlled the accumulation of organic matter
during siliceous shale deposition. The strong correlation of
TOC vs. Th/U (R2 = 0.75) and TOC vs. Mo (R2 = 0.68) implies
that the organic carbon accumulations was mainly due to an-
oxic water column.
Acknowledgements
The authors express their gratitude to Prof. Quanyou Liu for his
comments and modifications in order to improve the manuscript.
This work was supported by China Postdoctoral Science Foundation
(No. 2016M591350). Comments and suggestions of Editors and re-
viewers are gratefully appreciated.
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