Beruflich Dokumente
Kultur Dokumente
Geosciences Department, Faculty of Geosciences and Petroleum Engineering, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia
Polytechnic of Geology and Mining Bandung. Jl. Sulaksana 21, Bandung, Indonesia
School of Physics, Universiti Sains Malaysia, 11800 USM Penang, Malaysia
a r t i c l e
i n f o
Article history:
Received 15 April 2016
Received in revised form 5 August 2016
Accepted 6 August 2016
Available online 10 August 2016
Keywords:
Black shales
Malaysia
Mineralogy
Geochemistry
Origin
Maturation
a b s t r a c t
Palaeozoic black shale-bearing formations comprise 25% of the sedimentary cover in Peninsular Malaysia. However, nothing has been published regarding their geology, composition and maturation. Representative samples
from different ages and localities of the black shales were subjected to detailed mineralogical and geochemical
investigations during this study to determine their origin. These investigations also provide an opportunity to
trace the changes in depositional environments and paleoclimate during the Palaeozoic as well as the nature
of unknown and hidden basement rocks in Malaysia.
This paper reports nineteen Palaeozoic formations in Malaysia that contain black shales that are classied into
seven categories based on their age. These are the Cambrian-Ordovician, Ordovician-Devonian, SilurianDevonian, Devonian, Carboniferous, Carboniferous-Permian and Permian black shales. Although illite was identied in all black shales, other clay minerals including kaolinite and smectite-illite mixed layers show signicant
variations among the studied samples. The Al2O3/TiO2 ratios (1333), SiO2 contents of probable magmatic source
rocks (5469 wt.%) and Zr-TiO2 bivariate diagram suggest a mixture of felsic and intermediate source rocks for
the studied black shales. This indicates that the hidden basement rocks in Malaysia are dominated by felsic igneous rocks. Variations in clay minerals, SiO2 and Al2O3/TiO2 ratios and upper continental crust (UCC)-normalized
REE patterns suggest a local provenance for each locality rather than regional and common source rocks for all
black shales. Al2O3/SiO2 ratios vary from one age to the other ranging between 0.09 and 0.37. This indicates
changes in the degree of weathering of the sediment-source rocks of these shales and suggests climate changes
in the Peninsular Malaysia during the Palaeozoic from relatively wet conditions during the Cambrian to relatively
dry conditions during the Ordovician followed by relatively wet conditions extends from the Silurian to the Carboniferous, which followed by relatively dry conditions during the formation of Carboniferous-Permian black
shales and nally to relatively wet conditions during the Permian. The V/Ni, V/(V + Ni) and V/(V + Cr) ratios
as well as the positive Ce anomalies indicate that these black shales were deposited under reducing conditions.
The high V/Ni ratios (N 3) also suggest a purely marine source input for the organic matter. Devonian black shales
show relatively high concentrations of redox-sensitive elements, which may suggest the possible existence of Devonian anoxia as well as the Devonian-Carboniferous (D-C) boundary in Malaysia. Based on the abundance of illite (N85%) and illite crystallinity (IC) values (27462), the majority of the Palaeozoic black shales in
Peninsular Malaysia are probably anchimetamorphic and over-matured.
2016 Elsevier B.V. All rights reserved.
1. Introduction
The geochemistry of black shales has played a major role in the characterization of both organic material and inorganic constituents, widening the scope of inferences drawn about the genesis of black shales.
Considerable progress has been made in understanding the geochemistry of black shales by going beyond traditional bulk analyses, placing an
emphasis on deciphering the speciation of elements (e.g. Yang et al.,
Corresponding author.
E-mail address: hassanbaioumy@hotmail.com (H. Baioumy).
http://dx.doi.org/10.1016/j.coal.2016.08.007
0166-5162/ 2016 Elsevier B.V. All rights reserved.
2004; Guo et al., 2007). Black shales have attracted interest from researchers primarily because of their economic importance in terms of
hydrocarbon development potential (i.e., source rocks) as well as
metal concentrations (Wignall, 1994). Black shales are also of interest
to geobiologists who are interested in the evolving redox conditions
on Earth as it relates to the evolution and extinction of life (e.g.
Wignall, 1994; Uffmann et al., 2012). During the last few years, considerable attention has been given to unconventional oil and gas shales
(e.g. Soua, 2014). Although Palaeozoic black shales are old and their organic contents and maturation might have been altered by diagenesis/
metamorphism, these shales attract interest from researchers as
91
92
Fig. 1. Geological map of Peninsular Malaysia showing the location of Palaeozoic black shale outcrops analyzed in this study. Location numbers (118) are listed in Table 1.
black carbonaceous shales (Fig. 4D) of early Devonian age (Meor Hakif
Hassan and Lee, 2005; Meor Hakif Hassan et al., 2014). The Chepor Formation is exposed in the Hutan Aji and Guar Jentik areas. It is subdivided
into two members, member CF-1 of fossiliferous mudstone interbedded
with thin sandstone and member CF-2 of dark grey to black mudstone
interbedded with thin siltstone, thin to medium thick beds of laminated,
pebbly or massive sandstone, and minor red mudstone, with black
mudstone facies. The Sanai Formation crops-out in the northern part
of Hill B in the Guar Gentic area overlying the red bed of the Chepor Formation in a conformable contact. It is composed of limestone intercalated with dark grey to black shales. The age of the Sanai Formation is late
Devonian (Meor Hakif Hassan and Lee, 2005).
2.2.5. Carboniferous
Carboniferous black shales occur in the Telaga Jatoh Formation of the
Perlis District (Fig. 3B), Kinta Valley in the Perak District, as well as the
Sungai Perlis Bed in the Terengganu District. The Telaga Jatoh Formation
crops-out in the northern part of Hill B in the Guar Gentic area overlying
the Sanai Formation (Fig. 3B). It is composed of yellowish-grey massive
restricted basin (Stauffer, 1973). The occurrences of ammonoid and crinoid stems (Abdullah Sani, 1985) as well as spores (Chen et al., 1995)
indicate the age of this formation to be of Carboniferous to Permian age.
2.2.7. Permian
Five Permian black shale outcrops representing the Permian in Peninsular Malaysia are present in the Sri Jaya (Sri Jaya Beds) and Bera (Bera
Formation) areas of the Pahang District, the Johor District (Dohol and
Mersing formations) and in the Kedah District (Semanggol Formation).
The Sri Jaya Beds, Kuantan Group (Henri and Bin, 1994) comprise of
black shale, claystone and sandstone. The Bera Formation consists predominantly of mudstone/shale, siltstone and sandstone, with subordinate conglomerate. The lower part of the formation is made-up of
massive mudstone, thick to massive tuffaceous sandstone, siltstone
and mudstone, and thinly-bedded siliceous mudstone. The upper part
of the formation consists of thinly to thickly bedded shale, siltstone,
sandstone and conglomerate. The faunal assemblage (brachiopods,
cephalopods, trilobites, bivalves, gastropods, fusulinids, plants and
trace fossils) indicates a general Middle Permian age for this formation
(Leman and Sone, 2000). Black shales in the Johor District belong to
the Mersing and Dohol formations. The Dohol Formation is composed
predominantly of argillaceous lithologies (grey to black carbonaceous
shale, mudstone, slate, phyllite and schist), with minor arenaceous lithologies and limestone, as well as associated contemporaneous volcanic rocks (Rajah, 1986) (Fig. 3). Based on fusulinids found in the
limestone unit, Igo et al. (1979) interpreted the age of this formation
as early to middle Permian. The Mersing Formation is the oldest rock
in eastern Johor, uncomformably overlain by all the other sedimentary
formations. The lithology of this formation consists of interbedded
black shale, quartzite, graphite and schist (Roslan, 2005). The
Semanggol Formation was introduced by Alexander (1950) for the sedimentary rocks exposed in the Semanggol range from north Perak. The
Palaeozoic black shales in the Semanggol Formation were reported in
the Permian part of the formation at Bukit Kukus, south Kedah as
nely-laminated black mudstone.
3. Materials and methods
Approximately 51 black shale samples were collected spanning various ages, localities horizons, and lithologies of the Palaeozoic black
shales from Peninsular Malaysia. Samples were taken either from relatively fresh faces in clay quarries or road cuts representing vertical and
lateral lithological and/or colour variations in the shales Depending on
the dimensions and accessibility of the individual outcrop. Weathered
parts in these samples, if any, were removed and samples were preserved in ladled plastic bags. Due to lack of analytical facilities, twenty
seven (27) of these 51 samples were selected for detailed mineralogical
and geochemical investigations representing various ages, formations,
localities and horizons based on their bulk mineralogy and lithology
(Fig. 1). For mineralogical analyses, both bulk samples and clay fractions
of the black shale samples were analyzed using X-ray diffraction (XRD).
Bulk black shale samples were ground in an agate mortar and mounted
in the X-ray holder. To separate the clay fractions, 10 g of the black
shales were transferred to 600 ml beakers and treated with dilute 1 M
acetic acid to remove carbonates. The residue was washed with distilled
water and then treated with 30% H2O2 to remove organic matter. After
each sample was completely disaggregated, it was washed with distilled
water several times until completely suspended. The suspended clay
fraction (b 2 m) was mounted on glass slides by dropper and left to
dry. For each sample, three oriented slides were prepared. One was untreated, a second saturated with ethylene glycol vapour at 60 C for 1 h,
and the fth heated at 550 C for 3 h. A Bruker D8 X-ray generator with
Ni-ltered Cu-K, run at 40 kV and 25 mA, was used to examine both
the bulk samples and the clay fractions. The scans were limited to the
range from 2 to 80 2 for the bulk samples and from 2 to 40 2 for
the clay fractions. Minerals identication was based on Moore and
93
94
Fig. 2. Stratigraphy of Palaeozoic units in Peninsular Malaysia A) Langkawi (after Cocks et al., 2005), B) Perlis and Kedah (after Meor Hakif Hassan and Lee, 2005), C) North Perak (after
Cocks et al., 2005), and D) Central Peninsular Malaysia (after Cocks et al., 2005).
4.2. Geochemistry
4.2.1. Major oxides
The distribution of major oxides in the Palaeozoic black shales from
Peninsular Malaysia is shown in Table 4. Silica and alumina represent
the major constituents in all samples except the Cambrian black shales
which show very low SiO2 and Al2O3 content due to the abundance of
carbonate. Carboniferous black shales have relatively low SiO2 contents,
while the Ordovician-Devonian black shales have the highest SiO2 contents. Permian black shales show relatively higher Al2O3, while the
Ordovician-Devonian black shales have the lowest Al2O3 contents
when compared with other black shales. K2O represents the third
major constituent and is relatively high in all analyzed black shales
and is related to the occurrence of illite. Generally, Carboniferous and
Permian black shales show relatively higher K2O contents when compared with other black shales. On the other hand, the OrdovicianDevonian black shales have the lowest K2O contents. Fe2O3 occurs in relatively low concentrations except in the Devonian and Carboniferous
black shales that show signicantly high Fe2O3 concentrations compared to other black shales. Other oxides such as CaO, MgO, Na2O,
TiO2, MnO and P2O5 generally occur in low concentrations (b1 wt.%).
Exceptions are the Cambrian black shales from Langkawi and the
black shale from the Sanai Formation, Perlis which show high CaO contents. The high CaO in the Cambrian black shales is due to the abundance
of calcite, while in the Sanai Formation it is due to the abundance of
dacryoconarid tentaculites fossils.
The major element composition of ne siliciclastic rocks is usually
controlled by clay minerals and non-clay silicate phases (Cox et al.,
1995; Moosavirad et al., 2011). In order to investigate the role of each
of the above factor in major elemental composition of the studied
shales, the values of the index of compositional variation (ICV; Cox
et al., 1995) are estimated. ICV values are estimated by the following
equation (Cox et al., 1995):
95
Table 1
Age, location and coordinates of Palaeozoic black shales from Peninsular Malaysia. Numbers (118) in this table correspond to the black shale outcrops in Fig. 1.
No.
Age
Formation
State
Sample
Latitude
Longitude
1.
2.
3.
4.
5.
6.
Permian
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Kubang Pasu
Pahang
034006.5
031226.41
015812.2
022727.8
5337.8
063318.52
1025253.6
1023645.47
1035041.5
1034923.9
100401.5
1001410.21
7.
Kati bed
Perak
045047.7
1005418.1
8.
9.
10.
11.
Kenny Hill
Kuala Lumpur
Sungai Perlis
Terengganu
025807.5
025047.9
5380.24
043944.57
1014317.9
1014852.5
1024015.79
103347.91
Batu Gajah
Telaga Jatoh
Sanai
Chepor
Perak
Perlis
SJ2
BFM
DH2.1
MRS
BK
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
042823.9
063318.00
1010423.3
1001224.00
053508
032556.4
33343.54
054440.1
053657
062559.6634
1014534
1020016.7
1015334.25
1010138.4
1010148
994111.9796
Carboniferous-Permian
Carboniferous
12.
13.
Devonian
14.
15.
Silurian-Devonian
16.
17.
18.
Ordovician-Devonian
Cambrian
Timah Tasoh
Bendang Riang
Karak
Balling
Kroh
Matchinchung
Johor
Kedah
Perlis
Perak
Pahang
Kedah
Langkawi (Kedah)
Fig. 3. Detailed stratigraphy of Palaeozoic successions in Peninsular Malaysia showing the ages and sampling horizons of blac8k shales. A) Cambrian black shales from Langkawi,
B) Devonian, Carboniferous and Permian black shales from Perlis, C) Carboniferous black shales from Terengganu, D) Permian black shales from Joho, and E) Carboniferous black shales
from Perak.
96
Fig. 4. Field photos of the Palaeozoic black shale outcrops in Peninsular Malaysia. A) Cambrian black shale outcrop from Langkawi, B) Ordovician-Devonian black shales outcrop from Baling, B) Silurian-Devonian black shale outcrop from Grik, C) Devonian black shales outcrop from Perlis, D) Carboniferous black shale outcrop from Perak, E) Carboniferous-Permian black
shale outcrop from Kuala Lumpur and F) Permian black shale outcrop from Johor.
The ICV values are quite similar in the Palaeozoic black shales in
Malaysia and vary from 0.19 to 0.79. Values of ICV b 1 are typical of minerals like kaolinite, illite, and muscovite and higher values (N1) are characteristic of rock-forming minerals such as plagioclase, K-feldspar,
amphiboles, and pyroxenes. Hence, the Palaeozoic black shales in
Malaysia are enriched in the phyllosilicates.
Assuming that Al2O3 represents the detrital fraction in the black
shales, the correlations between Al2O3 and other major oxides have
been examined. All black shales possess negative correlations between
Al2O3 and SiO2 that can be related to quartz dilution during transportation (e.g. Kampunzu et al., 2005; Deru et al., 2007; Moosavirad et al.,
2011). On the other hand, all black shales exhibit positive correlations
between Al2O3 and TiO2 suggesting the occurrence of TiO2 as an essential chemical component of the clay minerals. Meanwhile, the correlations between Al2O3 and K2O vary among the studied black shales.
Silurian-Devonian and Carboniferous black shales show positive correlations. These variations are probably due to the variations in the host
mineral of both Al2O3 and K2O in these shales. The positive correlations
indicate the occurrence of K2O entirely in the illite, while in other shales,
K2O may occur in other phase(s) in addition to illite.
4.2.2. Trace elements
The distribution of trace elements in the Palaeozoic black shales
from different ages is listed in Table 5. Barium records the highest concentrations in all black shales with averages ranging from 407 to
1253 ppm. Cr, Rb, Sr, V and Zr occur in relatively high concentrations
compared to other trace elements with averages of N 100 ppm in all
black shales. Cu, Pb, Zn, Ni, Sc, Ga, Hf, Nb and Y occur in relatively low
concentrations with averages of b100 ppm. The rest of the elements
show low concentrations relative to other trace elements with averages
97
Table 2
Mineralogical composition of the Palaeozoic black shales from Peninsular Malaysia.
Age
Permian
Carboniferous-Permian
Formation
Sample
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Kubang Pasu
SJ2
BFM
DH2
MRS
BK
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
Kati bed
Kenny Hill
Carboniferous
Devonian
Silurian-Devonian
Ordovician-Devonian
Cambrian
Sungai Perlis
Batu Gaja
Tlaga Jatoh
Sanai
Chepor
Temah Tasoh
Bendang Riang
Karak
Balling
Kroh
Matchinchung
Non-clay minerals
Calcite
Pyrite
Illite
Kaolinite
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Minor
Major
Major
Traces
Traces
Traces
Minor
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Minor
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Minor
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Major
Minor
Major
Major
Major
Minor
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
Traces
below 10 ppm. When compared with other black shales from this study,
the Cambrian black shale sample shows low concentrations of all elements except for Sr due to the high carbonate content of this shale.
Ordovician-Devonian black shales show the highest Cr contents
among the studied black shales. Devonian black shales have the highest
Table 3
Illite crystallinity (IC) of the Palaeozoic black shales from Peninsular Malaysia.
Age
Formation
Sample
Permian
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Average
Kubang Pasu
SJ2
BFM
DH2
MRS
BK
0.38
0.27
0.32
0.38
0.46
0.36
0.32
0.32
0.32
0.27
0.46
0.32
0.32
0.34
0.38
0.32
0.32
0.32
0.32
0.34
0.27
0.32
0.42
0.38
0.35
0.32
0.46
0.32
0.37
0.27
0.32
0.30
0.27
Carboniferous-Permian
Kati bed
Kenny Hill
Carboniferous
Devonian
Silurian-Devonian
Ordovician-Devonian
Cambrian
Average
Sungai Perlis
Batu Gaja
Tlaga Jatoh
Average
Sanai
Chepor
Temah Tasoh
Average
Bendang Riang
Karak
Average
Balling
Kroh
Average
Matchinchung
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
Clay minerals
Quartz
concentrations of several trace elements including Mo, Cu, Pb, Zn, Ni, Se,
Ba, and U when compared with other Palaeozoic black shales in Peninsular Malaysia. Carboniferous black shales are enriched in As and Co relative to other black shales. Carboniferous-Permian black shales exhibit
the highest V contents, while Permian black shales exhibit the highest
Ga and Rb contents among the analyzed samples.
Correlation coefcients (r2) between trace elements and major oxides have been calculated. Al2O3 exhibits strong positive correlations
with Sc, Ga, Rb, Ta, and Th and weak positive correlations with Hf and
Nb. Fe2O3 has strong positive correlations with Zn, Ni, and Co. CaO
shows weak positive correlations with Sr. K2O shows relatively strong
positive correlations with Ga, Nb, Rb, Ta and Th. TiO2 shows strong positive correlations with Sc, Ga, Nb, Rb, Ta and Th as well as weak positive
correlations with Hf. P2O5 has a positive correlation with Ba.
4.2.3. Rare earth elements
The distribution of rare earth elements (REE) in the Palaeozoic black
shales from Peninsular Malaysia is shown in Table 6. Average sum of
rare earth elements (REE) ranges between 31 and 325 ppm. Samples
from the Permian black shales show the highest REE (325 ppm),
while the Cambrian black shales have the lowest REE value
(31 ppm). Carboniferous and Permian black shales show positive correlations between Al2O3 and REE. On the other hand, REE has no correlations with Al2O3 in the rest of the black shales. REE in the studied black
shales are normalized to values for the UCC as reported by Taylor and
Mclennan (1985) (Fig. 5). In comparison with the UCC, three enrichment types of REE are generally identied (Seredin and Dai, 2012): Ltype (light-REE; LaN/LuN N 1), M-type (medium-REE; LaN/SmN b 1,
GdN/LuN N 1), and H-type (heavy REE; LaN/LuN b 1). Additionally, normal type (N-type) of REE distribution patterns represent very weak or
no fractionation among the L-, M-, and H-REE. Accordingly, the majority
of the Palaeozoic black shales from Peninsular Malaysia are classied as
H-type where LaN/LuN b 1 ranging from 0.34 to 0.71. Exceptions are one
sample from the Permian black shales (Sri Jaya Formation), one sample
from the Carboniferous black shales (Telaga Jatoh Formation), one sample from the Devonian black shales (Chepor Formation), two samples
from the Silurian-Devonian black shales (Bendang Riang and Karak
98
Table 4
Major oxides (wt.%), CIA, Al/Ti ratios and TOC contents (wt.%) of the Palaeozoic black shales from Peninsular Malaysia.
Age
Formation
Sample
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI
Total
Al2O3/SiO2
Al2O3/TiO2
TOC
Permian
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Average
Kubang Pasu
SJ2
BFM
DH2
MRS
BK
55.41
64.74
58.67
63.84
72.34
63.00
70.96
62.21
74.01
74.69
60.78
79.66
61.60
69.13
69.91
60.19
72.44
75.07
53.22
66.17
51.42
58.99
53.00
76.96
60.09
82.32
61.17
72.98
72.16
92.48
70.34
81.41
8.31
0.95
0.62
0.98
0.91
0.86
0.86
0.70
1.01
0.70
0.60
0.95
0.51
1.02
0.78
0.81
0.99
0.70
0.66
1.20
0.87
0.78
0.72
0.93
0.23
0.67
0.46
1.06
0.69
0.74
0.11
0.64
0.38
0.09
27.91
20.59
26.78
22.27
15.52
22.61
12.49
16.42
11.12
7.93
16.54
8.42
18.69
13.09
18.66
25.15
17.51
12.26
21.66
19.05
15.17
16.05
21.30
5.21
14.43
8.60
24.10
14.49
15.73
3.34
10.29
6.82
1.64
0.75
0.54
0.53
0.52
0.88
0.64
2.86
4.56
2.75
1.09
2.49
0.31
1.58
2.23
0.82
0.97
0.48
0.98
5.28
1.71
4.79
7.93
7.99
2.12
5.71
1.45
0.88
0.78
1.04
0.53
1.42
0.98
0.50
0.01
0.01
0.01
0.01
0.01
0.01
0.03
0.02
0.02
0.02
0.02
0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.03
0.72
0.25
0.01
0.25
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.54
0.58
0.33
0.34
0.73
0.50
1.29
1.83
0.95
0.83
0.91
0.59
1.45
1.12
0.40
0.58
0.16
1.27
1.08
0.70
1.63
1.83
2.62
0.28
1.59
0.38
0.36
0.64
0.46
0.05
1.23
0.64
1.07
0.02
0.01
0.02
0.01
0.01
0.01
1.33
0.80
0.38
0.03
0.03
0.01
0.04
0.37
0.01
0.01
0.01
0.01
0.13
0.03
6.86
0.28
0.06
0.08
1.82
0.05
0.01
0.01
0.02
0.02
0.01
0.02
47.6
0.07
0.18
0.70
0.59
0.06
0.32
1.42
0.86
0.50
0.02
0.02
0.05
0.04
0.42
0.18
0.18
0.27
0.04
0.04
0.14
0.06
0.09
0.07
0.03
0.06
0.02
0.21
0.06
0.10
0.02
0.02
0.02
0.01
3.80
5.40
5.16
5.25
3.33
4.59
4.02
6.14
4.86
1.94
2.27
2.65
5.20
3.87
4.56
5.96
2.88
3.87
6.72
4.80
5.28
4.72
5.85
1.47
4.33
0.95
4.35
3.11
2.80
0.16
3.51
1.84
0.69
0.11
0.01
0.03
0.06
0.02
0.05
0.10
0.13
0.07
0.12
0.10
0.04
0.13
0.10
0.02
0.01
0.01
0.01
0.05
0.02
0.17
0.09
0.05
0.42
0.18
0.51
0.03
0.02
0.19
0.02
0.04
0.03
0.01
10.20
7.10
6.60
5.90
6.10
7.18
4.60
5.80
4.40
12.40
15.50
7.10
9.90
8.53
4.50
5.70
5.40
5.70
10.30
6.32
13.50
8.30
7.60
12.70
10.53
4.70
7.60
7.00
6.43
3.20
12.10
7.65
39.90
99.76
99.82
99.78
99.70
99.84
99.78
99.82
99.79
99.80
99.69
99.68
99.35
99.67
99.69
99.85
99.78
99.85
99.83
99.76
99.81
99.74
99.78
99.77
99.50
99.70
99.44
99.82
99.83
99.70
99.97
99.66
99.82
99.90
0.50
0.32
0.46
0.35
0.21
0.37
0.18
0.26
0.15
0.11
0.27
0.11
0.30
0.20
0.27
0.42
0.24
0.16
0.41
0.30
0.30
0.27
0.40
0.07
0.26
0.10
0.39
0.20
0.23
0.04
0.15
0.09
0.20
29.38
33.21
27.33
24.47
18.05
26.17
17.84
16.26
15.89
13.22
17.41
16.51
18.32
16.69
23.04
25.40
25.01
18.58
18.05
21.84
19.45
22.29
22.90
22.65
21.70
18.70
22.74
21.00
21.35
30.36
16.08
18.17
18.22
1.0
2.3
0.9
2.4
1.4
1.6
1.4
1.2
0.8
5.2
5.9
4.1
3.9
3.2
2.5
0.3
0.3
1.9
3.1
1.6
4.9
1.7
1.1
6.9
3.7
2.4
1.2
2
1.9
0.9
8.2
4.6
0.5
Carboniferous-Permian
Kati bed
Kenny Hill
Carboniferous
Devonian
Silurian-Devonian
Ordovician-Devonian
Cambrian
Average
Sungai Perlis
Batu Gaja
Tlaga Jatoh
Average
Sanai
Chepor
Temah Tasoh
Average
Bendang Riang
Karak
Average
Balling
Kroh
Average
Matchinchung
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
Table 5
Trace elements (ppm) of the Palaeozoic black shales from Peninsular Malaysia.
Formation
Sample
Mo
Cu
Pb
Zn
Ni
As
Cr
Ba
Co
Ga
Hf
Nb
Rb
Sr
Ta
Th
Zr
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Average
Kubang Pasu
SJ2
BFM
DH2
MRS
BK
0.3
0.3
0.1
0.2
2.6
0.7
0.3
0.3
0.4
8.9
21.8
7.9
2.9
6.1
0.1
0.1
0.4
1.5
4.9
1.4
20.3
0.2
30.6
36.1
21.8
3.6
0.1
3.0
2.2
3.3
10.1
6.7
0.4
3.0
5.0
2.0
13.3
40.4
12.7
14.2
16.6
15.7
70.9
86.5
1.1
16.8
31.7
1.1
0.7
1.6
3.5
111.1
23.6
73.9
38.3
42.2
34.9
47.3
47.2
0.7
20.1
22.7
2.6
23.6
13.1
1.9
10.1
57.5
13.4
22.1
23.2
25.3
9.4
14.6
35.3
25.5
27.9
13.5
39.4
23.7
2.8
2.4
2.9
83.9
54.8
29.4
38.0
16.4
35.0
180
67.3
22.5
4.4
58.6
28.5
7.0
164
85.3
3.8
2
10
1
1
2
3.2
159
34
96
10
16
1
4
45.7
1
1
1
3
54
12
115
78
154
20
91.8
1
1
1
4.7
1
5
3
2
2.5
1.7
0.4
0.2
2.4
1.4
19.6
27.1
20.6
22.6
22.7
0.6
4.6
16.8
0.1
0.3
0.3
1.1
37.2
7.8
98.9
127.5
75.1
23.8
81.3
2.5
0.4
2.4
1.8
0.4
5.5
3.0
2.5
8.0
2.7
0.7
1.1
9.4
4.4
10.6
16.2
6.2
7.5
20.3
1.1
6.4
9.8
0.5
5.4
3.2
5.4
330.8
69.1
54.2
104.4
44.7
15.4
54.7
30.8
1.6
11.5
14.6
7.6
0.5
4.1
2.8
88.9
47.9
88.9
95.8
82.1
80.7
54.7
102.6
54.7
191.6
253.2
246.3
218.9
160.3
68.4
88.9
41.1
54.7
171.1
84.8
136.8
68.4
116.3
75.3
99.2
130.0
130.0
95.8
118.6
13.7
314.7
164.2
13.7
669
850
783
960
406
733
472
542
384
342
315.0
1063
795
559
564
840
529
574
353
572
377
643
447
3258
1181
3426
724
626
1592
117
698
407
51
1.9
2.4
1.2
0.3
4.4
2.0
9.4
14.2
12.3
2.9
1.9
0.2
1.8
6.1
0.6
0.9
1.6
0.8
3.5
1.5
13.6
39.0
28.8
3.9
21.3
0.7
1.0
2.4
1.4
0.4
1.4
0.9
2.0
29.5
25.0
34.8
30.0
20.3
27.9
15.5
23.4
15.5
16.9
25.4
17.4
29.1
20.5
23.7
29.3
21.8
17.1
44.5
27.3
19.3
21.7
27.0
9.4
19.4
13.1
27.3
20.7
20.4
5.0
17.1
11.1
2.7
10.9
6.2
8.1
10.4
5.9
8.3
8.1
8.2
12.7
4.9
6.3
3.9
6.5
7.2
7.3
8.6
9.6
4.0
7.3
7.4
5.0
5.0
3.8
1.6
3.9
3.0
8.3
3.3
4.9
2.2
3.7
3.0
0.5
16.2
12.0
28.3
28.4
19.6
20.9
18.0
29.2
23.5
19.8
25.2
14.7
27.1
22.5
17.7
22.4
19.7
14.4
25.2
19.9
17.1
25.2
24.2
7.0
18.4
10.9
20.5
17.5
16.3
2.6
15.4
9.0
2.0
259.6
222.6
277.8
293.7
140.1
238.8
115.2
176.2
122.9
127.4
153.1
116.5
233.4
149.2
191.8
264.8
176.9
177.9
218.7
206.0
159.6
178.5
207.3
53.8
149.8
99.6
233.0
162.2
164.9
20.4
135.0
77.7
17.2
133.9
37.8
88.2
115.7
40.6
83.2
106.0
68.7
63.1
150.1
106.7
12.6
162.3
95.6
70.9
32.7
46.3
13.0
39.3
40.4
105.2
46.4
41.2
89.0
70.5
399.5
63.4
18.9
160.6
12.1
44.3
28.2
458.9
1.5
1.0
2.2
2.4
1.6
1.7
1.3
2.3
1.7
1.3
1.9
1.0
1.8
1.6
1.4
1.8
1.7
1.0
1.8
1.5
1.3
1.9
1.8
0.6
1.4
0.8
1.7
1.4
1.3
0.1
1.2
0.7
0.2
33.1
17.5
29.4
35.8
16.4
26.4
13.8
20.9
14.1
15.4
18.3
13.6
26.9
17.6
17.3
20.6
27.4
11.4
30.6
21.5
22.1
22.3
33.9
8.0
21.6
13.1
21.6
16.8
17.2
4.5
13.2
8.9
2.3
5.3
4.2
4.0
8.4
3.8
5.1
1.7
2.3
2.3
13.4
11.9
8.7
9.8
7.2
3.8
4.1
4.2
4.6
10.9
5.5
13.5
1.7
4.3
13.4
8.2
6.4
4.5
4.5
5.1
1.7
12.9
7.3
1.0
137
126
124
304
134
165
97
181
96
900
919
2631
496
760
150
184
69
239
370
202.4
458
126
179
411
293.5
286
173
234
231
17
903
460
8
3.0
2.0
4.9
5.8
2.6
3.7
1.1
2.4
1.3
2.7
3.4
2.9
4.8
2.7
4.0
3.9
3.6
2.1
4.1
3.5
1.9
2.7
2.5
1.8
2.2
4.8
3.2
2.0
3.3
1.0
2.4
1.7
0.5
338.5
207.2
276.5
354.3
227.0
280.7
300.4
300.3
537.2
210.1
264.5
195.7
266.1
296.3
269.0
303.8
334.6
149.6
274.9
266.4
192.7
181.6
139.3
81.3
148.7
126.7
293.5
128.0
182.7
91.3
162.7
127.0
20.6
48.9
20.6
49.9
61.1
26.9
41.5
26.8
31.9
32.3
60.5
43.9
57.8
72.6
46.5
11.5
39.8
33.0
24.7
37.6
29.3
36.8
36.3
26.6
35.9
33.9
57.4
18.3
27.2
34.3
7.2
35.7
21.5
5.3
Carboniferous-Permian
Kati bed
Kenny Hill
Carboniferous
Devonian
Silurian-Devonian
Ordovician-Devonian
Cambrian
Average
Sungai Perlis
Batu Gaja
Tlaga Jatoh
Average
Sanai
Chepor
Temah Tasoh
Average
Bendang Riang
Karak
Average
Balling
Kroh
Average
Matchinchung
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
Age
Permian
99
100
Table 6
Rare earth elements (ppm) of the Palaeozoic black shales from Peninsular Malaysia.
Age
Formation
Sample
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Sum
Permian
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Average
Kubang Pasu
SJ2
BFM
DH2
MRS
BK
112.9
26.7
76.7
85.1
48.7
70.0
39.8
48.3
45.7
68
54.3
38.7
87.9
54.7
20
62.3
26.4
45.2
78.1
46.4
51.3
39.3
73.3
28.4
48.1
109
38.5
53.9
67.1
14.8
45.1
30.0
6.7
229.3
61.5
150.4
162.1
120.8
144.8
83.9
100.1
96.8
116.8
96.3
66.6
165.1
103.7
22.6
121.4
44.5
83.6
149.5
84.3
101.3
93
166
56
104.1
134.6
79.3
111.7
108.5
18.3
72.2
45.3
12.9
24.15
6.81
17.17
18.7
11.05
15.6
9.03
10.88
10.9
16.01
12
8.03
19.77
12.4
2.59
14.12
4.52
10.03
16.1
9.5
11.32
9.09
15.86
7.2
10.9
21.16
7.66
11.54
13.5
2.71
8.53
5.6
1.51
81.8
25.7
59.3
68.8
39.1
54.9
32.7
41.1
40.7
62.3
43.6
27.8
74
46.0
6.8
50.7
15.7
37.2
57.7
33.6
42.4
37.3
53.2
27.9
40.2
77.3
26.8
40.1
48.1
9.5
30.2
19.9
5.6
13.33
4.74
10.76
12.06
6.9
9.6
6.04
7.44
8.39
12.01
7.75
5.13
14.52
8.8
1.01
8.76
2.75
6.38
7.86
5.4
7.4
8.52
9.87
4.69
7.6
14.62
4.34
7.09
8.7
1.83
4.67
3.3
0.99
1.77
0.81
1.89
2.21
1.32
1.6
1.15
1.33
1.58
2.42
1.41
0.82
2.97
1.7
0.24
1.63
0.5
1.24
1.04
0.9
1.22
1.74
1.48
0.89
1.3
2.93
0.78
1.34
1.7
0.35
0.82
0.6
0.23
11.28
3.59
9.92
12.38
6.03
8.6
5.69
6.59
7.18
12.49
6.99
6
14.13
8.4
1.18
7.68
3.81
5.65
5.97
4.9
6.52
8.74
7.38
4.62
6.8
12.6
3.42
6.32
7.4
1.85
4.55
3.2
1.12
1.62
0.53
1.58
1.93
0.86
1.3
0.91
1.03
1.13
1.79
1.09
1.04
2.23
1.3
0.23
1.17
0.73
0.8
0.93
0.8
0.99
1.29
1.06
0.7
1.0
1.88
0.53
0.88
1.1
0.28
0.73
0.5
0.18
9.36
3.54
8.85
10.9
5.02
7.5
4.98
5.78
6.18
10.47
6.69
6.58
12.46
7.6
1.65
7.16
4.51
4.36
5.64
4.7
5.69
6.62
5.95
4.24
5.6
10.47
3.15
4.61
6.1
1.43
4.86
3.1
0.99
1.7
0.72
1.83
2.15
0.91
1.5
0.98
1.14
1.16
2.03
1.44
1.53
2.38
1.5
0.38
1.45
1.05
0.8
1.16
1.0
1.14
1.22
1.02
0.9
1.1
1.85
0.61
0.85
1.1
0.24
1.08
0.7
0.18
4.81
2.43
5.22
6.27
2.61
4.3
2.74
3.42
3.24
6.09
4.62
4.86
6.67
4.5
1.55
4.29
3.23
2.44
3.77
3.1
3.08
3.51
2.68
2.62
3.0
4.96
2.14
2.4
3.2
0.55
3.54
2.0
0.47
0.75
0.41
0.75
0.96
0.42
0.7
0.44
0.53
0.51
0.91
0.72
0.73
1
0.7
0.27
0.67
0.53
0.38
0.57
0.5
0.5
0.53
0.45
0.4
0.5
0.65
0.37
0.37
0.5
0.1
0.61
0.4
0.08
4.81
2.88
5.22
6.24
2.71
4.4
2.71
3.47
3.35
6.02
5.18
4.96
6.35
4.6
2.21
4.52
3.55
2.47
3.57
3.3
3.19
3.26
2.76
2.59
3.0
4.05
2.86
2.56
3.2
0.51
4.31
2.4
0.47
0.81
0.48
0.83
0.95
0.41
0.7
0.43
0.53
0.51
0.96
0.84
0.85
0.94
0.7
0.39
0.72
0.59
0.42
0.56
0.5
0.47
0.5
0.42
0.42
0.5
0.53
0.5
0.38
0.5
0.08
0.71
0.4
0.07
498.39
140.84
350.42
390.75
246.84
325.45
191.5
231.64
227.33
318.3
242.93
173.63
410.42
256.54
61.1
286.57
112.37
200.97
332.47
198.70
236.52
214.62
341.43
141.57
233.54
396.6
170.96
244.04
270.53
52.53
181.91
117.22
31.49
Carboniferous-Permian
Kati bed
Kenny Hill
Carboniferous
Devonian
Silurian-Devonian
Ordovician-Devonian
Cambrian
Average
Sungai Perlis
Batu Gaja
Tlaga Jatoh
Average
Sanai
Chepor
Temah Tasoh
Average
Bendang Riang
Karak
Average
Balling
Kroh
Average
Matchinchung
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
Age
Formation
Sample
LaN/LuN
LaN/SmN
GdN/LuN
Ce/Ce*N
Eu/Eu*N
Permian
Sri Jaya
Bera
Dohol
Mersing
Semanggol
Average
Kubang Pasu
SJ2
BFM
DH2
MRS
BK
1.07
0.43
0.71
0.69
0.91
0.76
0.71
0.70
0.69
0.54
0.50
0.35
0.72
0.60
0.39
0.66
0.34
0.83
1.07
0.66
0.84
0.60
1.34
0.52
0.82
1.58
0.59
1.09
1.08
1.42
0.49
0.95
0.73
1.27
0.84
1.07
1.06
1.06
1.06
0.99
0.97
0.82
0.85
1.05
1.13
0.91
0.96
2.97
1.07
1.44
1.06
1.49
1.61
1.04
0.69
1.11
0.91
0.94
1.12
1.33
1.14
1.20
1.21
1.45
1.33
1.02
0.84
0.45
0.72
0.79
0.89
0.74
0.80
0.75
0.85
0.79
0.50
0.43
0.91
0.72
0.18
0.65
0.39
0.81
0.65
0.54
0.84
1.06
1.06
0.67
0.91
1.44
0.41
1.01
0.95
1.40
0.39
0.89
0.97
2.33
1.77
2.31
2.49
1.94
2.16
1.96
2.02
2.08
2.42
2.05
2.03
2.64
2.17
1.61
2.10
1.87
1.91
1.97
1.89
2.00
2.16
2.04
1.85
2.01
2.46
1.77
1.95
2.06
1.64
1.87
1.75
1.59
1.07
0.43
0.71
0.69
0.91
0.76
0.71
0.70
0.69
0.54
0.50
0.35
0.72
0.60
0.39
0.66
0.34
0.83
1.07
0.66
0.84
0.60
1.34
0.52
0.82
1.58
0.59
1.09
1.08
1.42
0.49
0.95
0.73
Carboniferous-Permian
Kati bed
Kenny Hill
Carboniferous
Devonian
Silurian-Devonian
Ordovician-Devonian
Cambrian
Average
Sungai Perlis
Batu Gaja
Tlaga Jatoh
Average
Sanai
Chepor
Temah Tasoh
Average
Bendang Riang
Karak
Average
Balling
Kroh
Average
Matchinchung
BC1
BC2
BC3
KB3
KB5
PUT2
NIL3
KBG
Paka2
Paka6
BG3
TJ
DHBS1
GMHA
AJ1
TTJA9
GR6
KP
BB1
BL5
PH1
M2
between ages but also between localities of the same age. If the studied
black shales were derived from the same source, they would exhibit
similar geochemical characteristics. These variations, therefore, suggest
a local provenance nearby the depositional basins of each black shales.
101
Fig. 5. Upper continental crust (UCC)-normalized patterns of rare earth elements (using UCC REE concentrations provided by Taylor and Mclennan (1985)) of the Palaeozoic black shale of
various ages from Peninsular Malaysia. (A) Cambrian, B) Ordovician-Silurian, C) Ordovician Devonian, D) Devonian, E) Carboniferous, F) Carboniferous-Permian, and G) Permian. All shales
exhibit relative enrichment of LREE over HREE and negative Eu anomalies.
have the lowest Al2O3/SiO2 ratios (average = 0.09), while the Permian
black shales show the highest Al2O3/SiO2 ratios (average = 0.37). The
Cambrian Silurian, Devonian and Carboniferous black shales exhibit
Al2O3/SiO2 ratios range from 0.19 to 0.29. This indicates changes in the
degree of weathering from one age to the other suggesting climate
changes in the Peninsular Malaysia during the Palaeozoic from relatively wet conditions during the Cambrian to relatively dry conditions during the Ordovician followed by relatively wet conditions extends from
the Silurian to the Carboniferous, which followed by relatively dry conditions during the formation of Carboniferous-Permian black shales and
nally to relatively wet conditions during the Permian (Fig. 7B).
102
Fig. 6. Positive correlations between TOC and Pb, U and V in the Palaeozoic black shales
from Peninsular Malaysia.
Fig. 7. A) The Palaeozoic black shales from Peninsular Malaysia plot in the felsic to intermediate igneous eld in the Zr-TiO2 bivariate discrimination diagram (McLennan et al., 1980).
B) Vertical variations in averages of Al2O3/SiO2 ratios among the Palaeozoic black shales from Peninsular Malaysia.
used the V/(V + Ni) and V/(V + Cr) ratios of N0.8 and 0.6, respectively
to indicate strong reducing conditions. Most of the analyzed samples
from the Palaeozoic black shales display V/(V + Ni) ratios of N0.8 and
V/(V + Cr) ratios of N 0.6 supporting a reducing environment during deposition. V/Ni ratio has been widely used to determine the degree of anoxia during deposition (e.g. Galarraga et al., 2008). V is usually enriched
in comparison with Ni in anoxic marine environments due to the strong
activities of the sulfate-reduction bacteria in this environment and the
relatively higher stability of vanadyl compared to nickel porphyrin complexes (e.g. Wanty and Goldhaber, 1992; Breit and Wanty, 1991; Peters
and Moldowan, 1993). According to Galarraga et al. (2008), a V/Ni ratio
higher than 3 indicates that the organic matter was deposited under reducing conditions, while V/Ni ratios ranging between 1.9 and 3 indicate
deposition under dysoxic-oxic conditions. The V/Ni ratios in the
Palaeozoic black shales are N3, indicating that these black shales were
deposited under reducing conditions. Galarraga et al. (2008) also suggested that V/Ni ratios N 3 indicates a marine origin of organic matter,
a V/Ni ratio ranging from 1.9 to 3 indicates mixed terrigenous and marine organic matter, while a V/Ni ratio b1.9 indicates predominantly terrigenous organic matter. The high V/Ni ratios (N 3) in the studied black
shales are suggestive of a solely marine source input for the organic
matter.
Large positive Ce anomalies in coals were used to indicate formation
of these coals in reducing conditions (e.g. Seredin, 1998; Ferenczi,
2001), while suboxic marine water is characterized by slight negative
Ce anomaly (Chen et al., 2015). The strong Ce anomalies in most of
the Palaeozoic black shales in Peninsular Malaysia conrms their marine
origin as well as prevailing reducing conditions during their formation.
The exceptional formations with negative Ce anomalies probably
formed under suboxic conditions.
5.3. Devonian anoxia and the Carboniferous boundary
The Devonian/Carboniferous (D/G) boundary event, also known as
the Hangenberg Event, has been widely recognized for a long time.
It represents a signicant extinction event that affected many pelagic
organisms with a generic extinction rate exceeding 45% (e.g. Walliser,
1984; Sepkoski, 1996). This increased burial of organic matter and globally widespread deposition of black shales at the end of the Devonian.
Although the ultimate cause for black shale deposition at the end of
the Devonian is unknown, the geochemical data of Kaiser et al. (2006)
supports the hypothesis that oceanic anoxia and increased organic matter inux can trigger mass extinctions, glaciations and eustatic sea-level
change. Devonian black shales show relatively high concentrations of
redox-sensitive elements such as V, Ni, Mo, U, Cu, Cr and Sb (e.g. Pi
et al., 2014; Adegoke et al., 2014) when compared with other Palaeozoic
black shales from Peninsular Malaysia, especially the Carboniferous
black shales. These data may suggest the possible existence of Devonian
anoxia and the Devonian-Carboniferous (D-C) boundary in Malaysia.
Detailed paleontological and isotopic investigations are necessary to
clarify this.
5.4. Black shale maturation
During progressive diagenesis and incipient metamorphism, illite, a
mica-like clay mineral, progressively attains a higher degree of internal
atomic order and a more denitive, muscovite-like, chemical formula. A
lack of K+ (Kisch, 1991) or an excess of Mg2+ and Ca2+ (Howard and
Roy, 1985) can hinder the transition of illite to muscovite. Kubler
(1967) introduced the crystallinity index (CI; or Kbler index, KI), 001
peak width at half height, reported in degrees 2, which is used widely
as an indication of diagenesis/metamorphism. Increasing diagenetic/
metamorphic grade increases illite crystallinity (decreasing IC values).
Therefore, the smectite to illite transformation and Illite Crystallinity
(IC) have been used by many authors to subdivide the diagenetic/lowgrade metamorphic zone (e.g. Frey, 1987; Rainer et al., 2002). The
103
104
Alexander, J.B., 1950. Progress report on geological work in southwest Pahang, Selangor
and Malacca. Geol. Sur. Malaysia. Ann. Rep. 1949, 230282.
Algeo, T.J., Maynard, J.B., 2004. Trace-element behavior and redox facies in core shales of
Upper Pennsylvanian Kansas-type cyclothems. Chem. Geol. 206, 289318.
Alias, F.L., Abdullah, W.H., Hakimi, M.H., Azhar, M.H., Kugler, R.L., 2012. Organic geochemical characteristics and depositional environment of the Tertiary Tanjong Formation
coals in the Pinangah area, onshore Sabah. Malaysia. Int. J. Coal Geol. 104, 921.
Azhar, H.H., Sivam, S.P., 1993. Locations of sedimentary basins in Peninsular Malaysia:
speculations on basement control, basin extension and hydrocarbon potential.
Warta Geologi 19 (6), 283284.
Bau, M., Dulski, P., 1996. Distribution of yttrium and rare-earth elements in the Penge and
Kuruman iron-formations, Transvaal Supergroup. South Africa. Precamb. Res. 79,
3755.
Berry, W.B.N., Boucot, A.J., 1972. Correlation of the Southeast Asian and Near Eastern Silurian rocks. Geol. Soc. Amer. Spec. 137, 165.
Breit, G.N., Wanty, R.B., 1991. Vanadium accumulation in carbonaceous rocks: a review of
geochemical controls during deposition and diagenesis. Chem. Geol. 91, 8397.
Burton, C.K., 1970. Geology and mineral resources of the Baling area, Kedah and Perak.
Geol. Surv. Dist. Mem. 12, 1829.
Burton, C.K., 1972. The geology and mineral resources of the Baling area, Kedah and Perak.
Geol. Sur. Malaysia Dist. Mem. 12, 1150.
Cardott, B.J., 2012. Thermal maturity of Woodford shale gas and oil plays, Oklahoma. USA.
Int. J. Coal Geol. 103, 109119.
Chand, F., 1978. The geology and mineral resources of the Ulu Paka area, Terengganu.
Geological survey of Malaysia 16. Distr. Mem. 1, 2056.
Chen, J., Algeo, T.J., Zhao, L., Chen, Z.-Q., Cao, L., Zhang, L., Li, Y., 2015. Diagenetic uptake of
rare earth elements by bioapatite, with an example from Lower Triassic conodonts of
South China. Earth Sci. Rev. 149, 181202.
Chen, X., Rong, J., Wang, X., Wang, Z., Zhang, Y., Zhan, R., 1995. Correlation of the Ordovician rocks of China. Int. Un. Geol. Sci. Publ. 31, 1104.
Cocks, L.R.M., Torsvik, T.H., 2002. Earth geography from 500 to 400 million years ago: a
faunal and palaeomagnetic review. J. Geol. Soc. Lond. 159, 631644.
Cocks, L.M.R., Fortey, R.A., R.A., Lee, C.P., 2005. A review of Lower and Middle Palaeozoic
biostratigraphy in west Peninsular Malaysia and southern Thailand in its context
within the Sibumasu terrane. J. Asian Earth Sci. 24, 703717.
Cox, R., Lowe, D.R., Cullers, R.L., 1995. The inuence of sediment recycling and basement
composition on evolution of mudrock chemistry in the southwestern United States.
Geochim. Cosmochim. Acta 59 (14), 29192940.
Dai, S., Graham, I.T., Ward, C.R., 2016. A review of anomalous rare earth elements and yttrium in coal. Int. J. Coal Geol. 159, 8295.
Dai, S., Li, T., Jiang, Y., Ward, C.R., Hower, J.C., Sun, J., Liu, J., Song, H., Wei, P., Li, Q., Xie, P.,
Huang, Q., 2015. Mineralogical and geochemical compositions of the Pennsylvanian
coal in the Hailiushu Mine, Daqingshan coaleld, Inner Mongolia, China: implications
of sediment-source region and acid hydrothermal solutions. Int. J. Coal Geol. 137,
92110.
Dai, S., Zhang, W., Ward, C.R., Seredin, V.V., Hower, J.C., Li, X., Song, W., Wang, X., Kang, H.,
Zheng, L., Wang, P., Zhou, D., 2013. Mineralogical and geochemical anomalies of late
Permian coals from the Fusui coaleld, Guangxi Province, southern China: inuences
of terrigenous materials and hydrothermal uids. Int. J. Coal Geol. 105, 6084.
Dellisanti, F., Pini, G.A., 2010. Use of Tmax as a thermal maturity indicatorin orogenic successions and comparison with clay mineral evolution. Clay Miner. 45, 115130.
Dellisanti, F., Pini, G., Tateo, F., Baudin, F., 2008. The role of tectonic shear strain on the
illitization mechanism of mixed-layers illite/smectite. A case study from a fault
zone in the northern Apennines, Italy. Int. J. Earth Sci. 97, 601616.
Deru, X., Xuexang, G., Pengehun, L., Guanghao, C., Bin, X., Bachinski, R., Zhuanli, H.,
Gonggu, F., 2007. MesoproterozoicNeoproterozoic transition: geochemistry, provenance and tectonic setting of clastic sedimentary rocks on the SE margin of the Yangtze block, South China. J. Asia Earth Sci. 29, 63650.
Dill, H., 1986. Metallogenesis of early Palaeozoic graptolite shales from the Graefenthal
Horst (northern Bavaria-Federal Republic of Germany). Econ. Geol. 81, 889903.
Dypvik, H., 1984. Geochemical compositions and depositional conditions of Upper Jurassic and Lower Cretaceous Yorkshire clays. England. Geol. Mag. 121 (5), 489504.
Ferenczi, P.A., 2001. Iron ore, manganese and bauxite deposits of the northern territory.
North. Territ. Geol. Surv. Rep. 13 (113 pp.).
Foo, K.Y., 1983. The Palaeozoic sedimentary rocks of Peninsular Malaysia-stratigraphy and
correlation. Proceedings of the Workshop on Stratigraphic Correlation of Thailand
and Malaysia 1, 119.
Foo, K.Y., 1990. Geology and mineral resources of the Taiping-Kuala Kangsar area, Perak
Darul Ridzuan. Geol. Sur. Map Rep. 1.
Fortey, R.A., Cocks, L.R.M., 2003. Palaeontological evidence bearing on global OrdovicianSilurian continental reconstructions. Earth Sci. Rev. 61, 245307.
Frey, M., 1987. Low Temperature Metamorphism. Chapman and Hall, New York (351 pp.).
Galarraga, F., Reategui, K., Martnez, A., Martnez, M., Llamas, J.F., Mrquez, G., 2008. V/Ni
ratio as a parameter in palaeoenvironmental characterisation of non-mature
medium-crude oils from several Latin American basins. J. Pet. Sci. Eng. 61, 914.
Guo, Q., Shields, G.A., Liu, C., Strauss, H., Zhu, M., Pi, D., Goldberg, T., Yang, X., 2007. Trace
element chemostratigraphy of two Ediacaran-Cambrian successions in South China:
implications for organosedimentary metal enrichment and silicication in the early
Cambrian. Palaeogeogr. Palaeoclimatol. Palaeoecol. 254 (12), 194216.
Hassan, M.H., Lee, C.P., 2002. Stratigraphy of the Jentik formation, the transitional sequence from the Setul limestone to the Kubang Pasu formation at Guar Sanai, Guar
Jentik, Beseri, Perlis-a preliminary study. Geol. Soci. Malaysia Bull. 45, 171178.
Hassan, M.H., Lee, C.P., 2005. The DevonianLower Carboniferous succession in Northwest
Peninsular Malaysia. J. Asian Earth Sci. 24, 719738.
Hassan, M.H., Aung, A., Becker, R.T., Rahman, N.A.A., Tham Fatt Ng, T.F., Ghani, A.A., Shuib,
M.K., 2014. Stratigraphy and palaeoenvironmental evolution of the mid- to upper
Palaeozoic succession in Northwest Peninsular Malaysia. J. Asian Earth Sci. 83, 6079.
Hayashi, K., Fujisawa, H., Holland, H., Ohmoto, H., 1997. Geochemistry of 1.9 Ga sedimentary rocks from northeastern Labrador, Canada. Geochim. Cosmochim. Acta 61
(19), 41154137.
He, B., Xu, Y.-G., Zhong, Y.-T., Guan, J.-P., 2010. The GuadalupianLopingian boundary
mudstones at Chaotian (SW China) are clastic rocks rather than acidic tuffs: implication for a temporal coincidence between the end-Guadalupian mass extinction and
the Emeishan volcanism. Lithos 119, 1019.
Henri, F., Bin, A.I., 1994. Biostratigraphy of the Kinta Valley, Perak. Seminar on PermoTriassic of Malaysia and Associated Mineralization 20 (2), 102103.
Howard, J.J., Roy, D.M., 1985. Development of layer charge and kinetics of experimental
smectite alteration. Clay Clay Miner. 33, 8188.
Hutchison, C.S., 1996. Geological evolution of South-East Asia. Geol. Soc. Malaysia 368.
Igo, H., Rajah, S.S., Kobayashi, F., 1979. Permian Fusulinaceans from the Sungei Sedili area,
Johore, Malaysia. Geol. Peleon. South. Asia 20, 95118.
Jaafar, A., 1976. The geology and mineral resources of the Karak and Temerloh area, Pahang. Geol. Sur. Dist. Mem. 15, 5267.
Jenner, G.A., Longerich, H.P., Jackson, S.E., Fryer, B.J., 1990. ICP-MSa powerful tool for
high-precision trace-element analysis in earth sciences: evidence from analysis of selected U.S.G.S. reference samples. Chem. Geol. 83, 133148.
Jones, C.R., 1970. The geology and mineral resources of the Grik area, Upper Perak. Geol.
Sur. Malaysia Dist. Mem. 11, 1144.
Jones, C.R., 1973. The Siluro-Devonian graptolite faunas of the Malay peninsula. Overs.
Geol. Min. Res. 44, 128.
Jones, C.R., 1981. The geology and mineral resources of Perlis, North Kedah and the
Langkawi Islands. Geol. Sur. Malaysia Dist. Mem. 17, 1257.
Jones, B., Manning, D.C., 1994. Comparison of geochemical indices used for the interpretation of palaeo-redox conditions in ancient mudstones. Chem. Geol. 111 (14),
111129.
Kaiser, S.I., Steuber, R.T., Becker, T., Joachimski, M.M., 2006. Geochemical evidence
for major environmental change at the Devonian-Carboniferous boundary in
the Carnic Alps and the Rhenish Massif. Palaeogeogr. Palaeoclimatol. Palaeoecol.
240, 146160.
Kampunzu, A.B., Cailteux, J.L.H., Moine, B., Loris, H.N.B.T., 2005. Geochemical characterization, provenance, source and depositional environment of Roches Argilo-Talqueuses
(TAR) and mines subgroups sedimentary rocks in the Neoproterozoic Katangan Belt
(Congo): lithostratigraphic implications. J. Afr. Earth Sci. 42, 11133.
Kisch, H.J., 1991. Illite crystallinity-recommendations on sample preparation, X-raydiffraction settings, and interlaboratory samples. J. Metamorph. Geol. 9, 665670.
Krumm, S., 1996. WINFIT 1.0 a computer program for X-ray diffraction line prole analysis. Acta Univ. Carol. Geol. 38, 253261.
Kubler, B., 1967. La cristallinite' de illite et les zones tout a` fait supe'rieures du
me'tamorphisme. Etages Tectoniques, Colloque de Neuchatel 1966. Universite
Neuchatel, Switzerland, pp. 105121.
Kubler, B., Jaboyedoff, M., 2000. Illite crystallinity. Comptes Rendus de l'Acadmie des Sciences Srie II 331, 7589.
Lane, H.R., Muller, K.J., Ziegler, W., 1979. Devonian and carboniferous conodonts from
Perak. Malaysia. Geolog. et Palaeontol. 13, 213226.
Lee, C.P., 1983. Stratigraphy of the Tarutao and Machinchang Formations. In: Nutalaya, P.
(Ed.), Stratigraphic Correlation of Thailand and Malaysia. Geological Societies of
Thailand and Malaysia, Bangkok, pp. 2038.
Lee, C.P., 2001. Occurrences of scyphocrinites loboliths in the Upper Silurian Upper Setul
limestone of Pulau Langgun, Langkawi, Kedah and Guar Sani, Berseri, Perlis. Proceedings Geological Society of Malaysia Annual Geological Conference 2001, 99104.
Leman, M.S., Sone, K.R.M.M., 2000. On the New Permian Bera formation from the Bera
District, Pahang, Malaysia. Geological Society of Malaysia Annual Geological Conference 2000, https://gsmpubl.les.wordpress.com/2014/10/agc2000_21.pdf.
McLennan, S.M., Nance, W.B., Taylor, S.R., 1980. Rare earth element-thorium correlation in
sedimentary rocks and the composition of the continental crust. Geochim.
Cosmochim. Acta 44, 18331839.
Merriman, R.J., Peacor, D.R., 1999. Very low-grade metapelites: mineralogy, microfabrics
and measuring reaction progress. In: Frey, M., Robinson, D. (Eds.), Low-Grade Metamorphism. Blackwell, Oxford, pp. 1060.
Metcalfe, I., 2013a. Gondwana dispersion and Asian accretion: tectonic and
palaeogeographic evolution of eastern Tethys. J. Asian Earth Sci. 66, 133.
Metcalfe, I., 2013b. Tectonic evolution of the Malay peninsula. J. Asian Earth Sci. 76,
195213.
Moore, D.M., Reynolds, R.C., 1997. X-ray Diffraction and the Identication and Analysis of
Clay Minerals. Oxford University Press, Oxford.
Moosavirad, S.M., Janardhana, M.R., Sethumadhav, M.S., Moghadam, M.R., Shankara, M.,
2011. Geochemistry of lower Jurassic shales of the Shemshak formation, Kerman
Province, Central Iran: provenance, source weathering and tectonic setting. Chem.
Erde 71, 279288.
Pashin, J.C., Kopaska-Merkel, D.C., Arnold, A.C., McIntyre, M.R., Thomas, W.A., 2012. Gigantic, gaseous mushwads in Cambrian shale: Conasauga formation, southern Appalachians, USA. Int. J. Coal Geol. 103, 7091.
Peters, K.E., Moldowan, J.M., 1993. The Biomarker Guide: Interpreting Molecular Fossils in
Petroleum and Ancient Sediments. Prentice-Hall, Inc., Englewood Cliffs, New Jersey.
Pi, D.H., Jiang, S.Y., Luo, L., Yang, J.H., Hong-Fei Ling, H.F., 2014. Depositional environments
for stratiform witherite deposits in the Lower Cambrian black shale sequence of the
Yangtze platform, southern Qinling region, SW China: evidence from redoxsensitive trace element geochemistry. Palaeogeogr. Palaeoclimatol. Palaeoecol. 398,
125131.
105
Uffmann, A.K., Littke, R., Rippen, D., 2012. Mineralogy and geochemistry of Mississippian
and Lower Pennsylvanian black shales at the northern margin of the Variscan Mountain Belt (Germany and Belgium). Int. J. Coal Geol. 103, 92108.
Walliser, O.H., 1984. Pleading for a natural D/C-boundary. Cour. Forschungsinst. Senck. 67,
241246.
Wanty, R.B., Goldhaber, M.B., 1992. Thermodynamics and kinetics of reactions involving
vanadium in natural systems: accumulation of vanadium in sedimentary rocks.
Geochim. Cosmochim. Acta 56, 14711483.
Warr, L.N., Rice, A.H.N., 1994. Interlaboratory standardization and calibration of clay mineral crystallinity and crystallite size data. J. Metamorph. Geol. 12, 141152.
Wignall, P.B., 1994. Black Shales: Oxford Monographs on Geology and Geophysics. 30.
Clarendon Press, Oxford, p. 127.
Yamamoto, K., Sugisaki, R., Arai, F., 1986. Chemical aspects of alteration of acidic tuffs and
their application to siliceous deposits. Chem. Geol. 55, 6176.
Yang, J.H., Jiang, S.Y., Ling, H.F., Feng, H.Z., Chen, Y.Q., Chen, J.H., 2004. Paleoceangraphic
signicance of redox-sensitive metals of black shales in the basal Lower Cambrian
Niutitang formation in Guizhou Province, South China. Prog. Nat. Sci. 14, 152157.
Zhou, C.M., Jiang, S.Y., 2009. Palaeoceanographic redox environments for the lower Cambrian Hetang formation in South China: evidence from pyrite framboids, redoxsensitive trace elements, and sponge biota occurrence. Palaeogeogr. Palaeoclimatol.
Palaeoecol. 271, 279286.