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Mineralogy and geochemistry of Palaeozoic

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International Journal of Coal Geology

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

Mineralogy and geochemistry of Palaeozoic black shales from Peninsular

Malaysia: Implications for their origin and maturation
Hassan Baioumy a,, Yuniarti Ulfa b, Mohd Nawawi c, Eswaran Padmanabhan a, Mohammad Noor Akmal Anuar c
a
Geosciences Department, Faculty of Geosciences and Petroleum Engineering, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia
b
Polytechnic of Geology and Mining Bandung. Jl. Sulaksana 21, Bandung, Indonesia
c
School of Physics, Universiti Sains Malaysia, 11800 USM Penang, Malaysia

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

Article history: Palaeozoic black shale-bearing formations comprise 25% of the sedimentary cover in Peninsular Malaysia. How-
Received 15 April 2016 ever, nothing has been published regarding their geology, composition and maturation. Representative samples
Received in revised form 5 August 2016 from different ages and localities of the black shales were subjected to detailed mineralogical and geochemical
Accepted 6 August 2016
investigations during this study to determine their origin. These investigations also provide an opportunity to
Available online 10 August 2016
trace the changes in depositional environments and paleoclimate during the Palaeozoic as well as the nature
Keywords:
of unknown and hidden basement rocks in Malaysia.
Black shales This paper reports nineteen Palaeozoic formations in Malaysia that contain black shales that are classied into
Malaysia seven categories based on their age. These are the Cambrian-Ordovician, Ordovician-Devonian, Silurian-
Mineralogy Devonian, Devonian, Carboniferous, Carboniferous-Permian and Permian black shales. Although illite was iden-
Geochemistry tied in all black shales, other clay minerals including kaolinite and smectite-illite mixed layers show signicant
Origin variations among the studied samples. The Al2O3/TiO2 ratios (1333), SiO2 contents of probable magmatic source
Maturation 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 igne-
ous 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 Car-
boniferous, 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 De-
vonian anoxia as well as the Devonian-Carboniferous (D-C) boundary in Malaysia. Based on the abundance of il-
lite (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 char-
acterization of both organic material and inorganic constituents, widen-
ing the scope of inferences drawn about the genesis of black shales.
Considerable progress has been made in understanding the geochemis-
try 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).
2004; Guo et al., 2007). Black shales have attracted interest from re-
searchers 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, consid-
erable attention has been given to unconventional oil and gas shales
(e.g. Soua, 2014). Although Palaeozoic black shales are old and their or-
ganic contents and maturation might have been altered by diagenesis/
metamorphism, these shales attract interest from researchers as

http://dx.doi.org/10.1016/j.coal.2016.08.007
0166-5162/ 2016 Elsevier B.V. All rights reserved.
 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105
potential unconventional energy resources (e.g. Schultz, 2004; Pashin
et al., 2012; Uffmann et al., 2012; Cardott, 2012; Soua, 2014).
Although Palaeozoic rocks represent about 25% of Peninsular
Malaysia and have been studied extensively for their geology and stra-
tigraphy (e.g. Burton, 1970; Jones, 1970; Foo, 1983, 1990), no publica-
tions have focused on the characteristics, geochemistry and origin of
the black shales in these successions. A few of the previous publications
that recognized black shales in these successions considered them as
slate or metamorphosed shales as expected from their ages (e.g.
Jaafar, 1976; Jones, 1970; Azhar and Sivam, 1993). Therefore, this
study was designed to address, for the rst time, the occurrence, geolo-
gy, mineralogy and trace and rare earth element geochemistry of these
black shales. These black shales cover all Palaeozoic ages from Cambrian
to Permian and thus provide a unique opportunity to examine the var-
iations in depositional environments as well as paleoclimate across the
Palaeozoic in Malaysia. The thermal maturity from the perspective of oil
and gas generation and possible metamorphism of these shales are also
discussed based on these data. The nature of unknown and hidden base-
ment rocks in Malaysia can be discussed through the investigations of
their source rock composition.
2. Geological setting
2.1. Stratigraphy of the Palaeozoic in Peninsular Malaysia
During the Early Palaeozoic, world geography was dominated by the
vast palaeocontinent of Gondwana. Around this lay a collage of much
smaller, but nevertheless substantial peri-Gondwanan terranes (Cocks
and Torsvik, 2002; Fortey and Cocks, 2003). One of these was the
Sibumasu (sometimes termed Shan-Thai) Terrane, which extended
from Burma (Myanmar) and south-west China in the north to Sumatra
in the south. Sibumasu is bounded to the east by the Uttaradit-Nan to
Raub-Bentong suture, which separates Sibumasu from the adjacent
Annamia (or Indochina) Terrane. To the west, Sibumasu is mostly
bounded today by the Andaman Sea, apart from the suture which lies
to the west of the Shan States in Burma. In the centre of the terrane
lay southern Thailand and western Peninsular Malaysia (e.g.
Sevastjanova et al., 2016).
The bulk of the Palaeozoic rocks of Malaysia are found in Peninsular
Malaysia, where they account for about 25% of the land area (Foo, 1983)
(Fig. 1). These Palaeozoic formations are distributed in four north-
westerly to northerly trending stratigraphic zones, namely (1) North-
western Zone, (2) Western Zone, (3) Central Zone, and (4) Eastern
Zone, all parallel to the general elongation trend of the peninsula (Lee,
2001). The rst two zones are sometimes combined into one to instead
give a three-fold division (e.g. Metcalfe, 2013a, 2013b). Early Palaeozoic
rocks are conned to the North-western and Western Zones, while the
occurrence of Late Palaeozoic rocks extends into and covers large tracts
of land in the Central and Eastern Zones (Foo, 1983). In other words, the
oldest rocks can be found at the north-western portion of the peninsula,
while relatively younger rocks can be found towards the southeast.
Cocks et al. (2005) divided the stratigraphy of Palaeozoic rocks in
Peninsular Malaysia into four areas (Fig. 2): (1) The Langkawi Islands;
(2) Kedah and Perlis; (3) north Perak; and (4) the central Peninsular
Malaysia area around Kuala Lumpur. The Palaeozoic in Langkawi Island
is represented by several formations including the Machinchang (Cam-
brian), Kaki Bukit Limestone (Ordovician), Tanjong Dendang (Ordovi-
cian), Mempelam Limestone (Silurian), Timah Tasoh (Devonian) and
Langgun Red bed (Devonian) formations. The Palaeozoic successions
in Kedah and Perlis start with the Cambrian metaquartzites of the
Jerai Formation followed by the lower to middle Ordovician Kaki Bukit
Limestone Formation. Meor Hakif Hassan and Lee (2002, 2005) and
Meor Hakif Hassan et al. (2014) recognized six Palaeozoic formations
in Perlis including the Mempelam Limestone, Timah Tasoh, Chepor,
Sanai, Telaga Jatoh and Kubang Pasu formations. At the base of the se-
quence in northern Perak, there is the undated Papulut Quartzite
91
overlain by thick variably bedded turbidite sequences, which have
been termed the Grik Formation, followed by the Bendong Riang For-
mation of phyllites and metamorphosed limestones. In the area near
Kuala Lumpur, in the Federal Capital area and neighbouring Selangor
State, there are a substantial number of named formations, notably
the Dinding Schist, which may be of Lower Palaeozoic age (Berry and
Boucot, 1972; Hutchison, 1996). To the north of Kuala Lumpur itself
there are some massive but weakly metamorphosed limestones and
marbles of Mid-Silurian age. Early Devonian graptolites are recorded
from deeper-water shales termed the Bentong Group in west Pahang.
From southern Perak, Lane et al. (1979) described successive
Devonian- Carboniferous conodont faunas from weakly metamor-
phosed carbonates termed the Kanthan Limestone in a heavily faulted
area near Kinta. Jones (1973) used the term Chemor Limestone for
these rocks, and they are associated with shales bearing biserial grapto-
lites of possible latest Ordovician age.
2.2. Occurrences of Palaeozoic black shales in Peninsular Malaysia
The Palaeozoic black shale-bearing formations in Peninsular
Malaysia are classied into seven groups based on their ages (Table 1,
Figs. 1, 3, 4).
2.2.1. Cambrian
The oldest stratigraphic formation in the Peninsular Malaysia is the
Machinchang Formation of Cambrian to early Ordovician age, which
can be found in north-western portion of Langkawi Island (Jones,
1981). Lee (1983) divided the formation into (1) the Lower member
(MF1), (2) the Middle member (MF2), and (3) the Upper member
(MF3). A thick interval of black carbonaceous and pyritiferous silty
shale had been reported from the middle portion of the Lower member
of Cambrian age (Figs. 3A, 4A).
2.2.2. Ordovician-Devonian
Two Ordovician-Devonian black shale outcrops were investigated
from Baling and Pengkalan Hulu areas of Kedah District that belong to
two formations; the Baling Formation and the Kroh Formation, respec-
tively. Burton (1970) identied ve main facies in the Baling Formation
including the arenaceous, limestone, argillaceous and calc-silicate fa-
cies. The black shales of the Baling Formation occur as part of the argil-
laceous facies and comprise dark grey to black shales and silty shales
(Fig. 4B). The Kroh Formation was the name introduced by Burton
(1972) and is composed of a sequence of black carbonaceous shale
and mudstone.
2.2.3. Silurian-Devonian
Three Silurian-Devonian black shale outcrops were investigated
from Peninsular Malaysia. Two of them are located in Pahang District
namely the Karak and Bentong areas and one in the Grik District. The
sedimentary covers in the Bentong and Karak localities belong to the
Karak Formation. Jaafar (1976) introduced the name Karak Formation
and divided it into ve facies, including (1) the rudaceous-arenaceous
facies, (2) the argillaceous facies, (3) the chert facies, (4) the limestone
facies, and (5) the pyroclastic facies. This formation consists predomi-
nantly of argillaceous rocks, which include dark grey to black carbona-
ceous shale (Fig. 4C) and phyllite, slate, schist, and hornfels. The
studied outcrop from Grik District belongs to the Bendang Riang Forma-
tion (Jones, 1970, 1973). This formation is composed mainly of carbona-
ceous shale with sandstone intercalations and phyllite, deposited in a
deeper water geanticline (Jones, 1973).
2.2.4. Devonian
The Devonian black shales were reported in three formations from
the Perlis District, northern Peninsular Malaysia namely, the Timah
Tasoh, Chepor, and Sanai formations (Fig. 3B). The lower Lalang mem-
ber of the Timah Tasoh Formation is composed predominantly of
92 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105
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 For-
mation 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 For-
mation in a conformable contact. It is composed of limestone intercalat-
ed 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
to weakly bedded chert with thin beds (few centimetres) of black to
dark grey claystone. Carboniferous black shale outcrops in the Perak
District occur in the Batu Gajah and Kuala Kangsar areas and are mainly
composed of grey and black aggy shales (Figs. 3C, 4E). A black shale-
bearing formation in the Terengganu District was reported from
Kampung Bintan and Ulu Paka areas and is named the Sungai Perlis
Beds (Chand, 1978). This formation consists of interbedded carbona-
ceous shales and sandstones (Fig. 3D).
2.2.6. Carboniferous-Permian
Carboniferous-Permian black shales are represented in this study by
the Kubang Pasu, Kati Beds and Kenny Hill formations. In the Kubang
Pasu Formation, black shales occur in three horizons separated by sand-
stones (Fig. 4F) in the Bukit Chondong area, Perlis District. Two
Carboniferous-Permian black shales outcrop at the Putrajaya and Nilai
areas and belong to the Kenny Hill Formation. This formation consists
of a monotonous sequence of interbedded phyllitic shale, mudstone
and sandstone, which are believed to have been deposited in the outer
portions of a delta or shelf, or upper portion of a submarine slope in a
 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105
restricted basin (Stauffer, 1973). The occurrences of ammonoid and cri-
noid 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 Pen-
insular 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 pre-
dominantly of mudstone/shale, siltstone and sandstone, with subordi-
nate 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 li-
thologies and limestone, as well as associated contemporaneous volca-
nic 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 sed-
imentary 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 var-
ious ages, localities horizons, and lithologies of the Palaeozoic black
shales from Peninsular Malaysia. Samples were taken either from rela-
tively 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 pre-
served 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 un-
treated, 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
Reynolds (1997). The illite crystallinity (IC) values were measured
using full width half maximum (FWHM) of the 001 illite peak by Expert
highscore software. IC data were calibrated against the CIS scale (Warr
and Rice, 1994) using the following regression equation: IC(CIS) = 0.93
IC(Bologna) + 0.09 (Dellisanti et al., 2008).
The same set of samples were analyzed for their major oxides, trace,
and rare earth elements at the ACME Lab., Canada. Fused discs prepared
for twenty seven representative samples were analyzed for their major
oxides (SiO2, TiO2, Al2O3, Fe2O3, MnO, MgO, CaO, K2O, Na2O, and P2O5)
by XRF using a Philips PW 2400 X-ray spectrometer. Tube voltage and
current were 40 kV and 60 mA, respectively. Loss on ignition (L.O.I.)
was obtained by heating sample powders to 1000 C for 6 h. Trace and
rare earth elements of twenty seven bulk samples were determined
by ICP-MS after digestion. The powders were completely dissolved in
HF (38%) and HNO3 (68%) in capped teon bombs on an electric hot
plate (~150 C) for 24 h. The solution was evaporated to near dryness,
and re-dissolved in 2 ml of 6 mol/l HNO3 in capped teon bombs at
150 C for two days. The samples were then evaporated near to dryness,
then 1 ml of 6 mol/l HNO3 was added, and the solutions were further di-
luted for analysis (e.g. Jenner et al., 1990).
TOC contents of the same set of samples were measured using a
Source Rock Analyzer (SRA-Weatherford) instrument at the Universiti
Malaya (UM), Malaysia following the method described in Alias et al.
(2012). Powdered samples were treated several times with 50 l of
50% sulfuric acid under a heat lamp at 6065 C and dried overnight at
~ 55 C in a drying oven to remove carbonates before being analyzed
at UM.
4. Results
4.1. Mineralogy
XRD analyses of bulk samples and clay fractions from the Palaeozoic
black shales from Peninsular Malaysia show wide variations in their
mineralogical compositions (Table 2). Cambrian black shales are com-
posed mainly of calcite and quartz with traces of pyrite as the non-
clay minerals, and illite and smectite-illite mixed layers as the clay min-
erals. Ordovician-Devonian black shales are made up of quartz, illite,
smectite-illite mixed layers and kaolinite. One sample from the Baling
Formation has more kaolinite and less illite compared to the black
shales from the Kroh Formation. The Silurian-Devonian black shales
consist of quartz, illite and kaolinite with trace smectite-illite mixed
layers in the black shale of the Bendang Riang Formation. Devonian
black shales from the Sanai Formation comprise calcite, quartz and illite
with traces of kaolinite, while the Devonian black shales from the Timah
Tasoh Formation are composed of quartz, illite, kaolinite, smectite-illite
mixed layers and traces of pyrite. Devonian black shales from the
Chepor Formation comprise quartz and illite, kaolinite and traces of
smectite-illite mixed layers. Carboniferous black shales from the Sungai
Perlis and Batu Gajah formations are composed of quartz, illite and some
kaolinite with traces of pyrite in the Batu Gajah Formation, while the
black shales from the Talgah Jatoh Formation are composed of quartz
and illite with traces of pyrite. Carboniferous-Permian black shales
from the Kenny Hill and Kati Bed formations are composed of quartz, il-
lite with some kaolinite and smectite-illite mixed layers, while the black
shales from the Kubang Pasu Formation are composed of quartz and il-
lite. All Carboniferous-Permian black shales have traces of pyrite.
Among the Permian black shales, The Semanggol, Dohol and Sri Jaya for-
mations are composed of quartz, illite and kaolinite, while the Mersing
and Bera formations are composed of quartz and illite with traces of
smectite-illite mixed layers and pyrite.
Values of illite crystallinity (IC) for the studied black shales range
from 0.27 to 0.462 (Table 3). The Cambrian and Ordovician-
Devonian black shales have relatively lower IC values (averages 0.27
and 0.302, respectively) compared with the rest of the studied
black shales (averages 0.34462).
94 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105
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 con-
tents. 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 com-
pared with other black shales. On the other hand, the Ordovician-
Devonian black shales have the lowest K2O contents. Fe2O3 occurs in rel-
atively low concentrations except in the Devonian and Carboniferous
black shales that show signicantly high Fe2O3 concentrations com-
pared 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 con-
tents. 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):
ICVFe2 O3 K2 O Na2 O Ca MgO MnO=Al2 O3
 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105 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. Permian Sri Jaya Pahang SJ2 034006.5 1025253.6

2. Bera BFM 031226.41 1023645.47
3. Dohol Johor DH2.1 015812.2 1035041.5
4. Mersing MRS 022727.8 1034923.9
5. Semanggol Kedah BK 5337.8 100401.5
6. Carboniferous-Permian Kubang Pasu Perlis BC1 063318.52 1001410.21
BC2
BC3
7. Kati bed Perak KB3 045047.7 1005418.1
KB5
8. Kenny Hill Kuala Lumpur PUT2 025807.5 1014317.9
9. NIL3 025047.9 1014852.5
10. Carboniferous Sungai Perlis Terengganu KBG 5380.24 1024015.79
11. Paka2 043944.57 103347.91
Paka6
12. Batu Gajah Perak BG3 042823.9 1010423.3
13. Telaga Jatoh Perlis TJ 063318.00 1001224.00
Devonian Sanai DHBS1
Chepor GMHA
AJ1
Timah Tasoh TTJA9
14. Silurian-Devonian Bendang Riang Perak GR6 053508 1014534
15. Karak Pahang KP 032556.4 1020016.7
BB1 33343.54 1015334.25
16. Ordovician-Devonian Balling Kedah BL5 054440.1 1010138.4
17. Kroh PH1 053657 1010148
18. Cambrian Matchinchung Langkawi (Kedah) M2 062559.6634 994111.9796

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 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105

A B

C D

E F

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 Bal-
ing, 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 min-
erals like kaolinite, illite, and muscovite and higher values (N1) are char-
acteristic 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 transporta-
tion (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 essen-
tial chemical component of the clay minerals. Meanwhile, the correla-
tions between Al2O3 and K2O vary among the studied black shales.
Silurian-Devonian and Carboniferous black shales show positive corre-
lations. 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 con-
centrations 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
 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105 97

Table 2
Mineralogical composition of the Palaeozoic black shales from Peninsular Malaysia.

Age Formation Sample Non-clay minerals Clay minerals

Quartz Calcite Pyrite Illite Kaolinite Smectite-illite mixed layers

Permian Sri Jaya SJ2 Major Traces Minor Major

Bera BFM Major Traces Major Traces
Dohol DH2 Major Major Major
Mersing MRS Major Major Traces
Semanggol BK Major Major Major
Carboniferous-Permian Kubang Pasu BC1 Major Traces Traces Major
BC2 Major Traces Traces Major
BC3 Major Traces Traces Major
Kati bed KB3 Major Traces Major
KB5 Major Traces Major
Kenny Hill PUT2 Major Traces Major Major Traces
NIL3 Major Traces Major Major Traces
Carboniferous Sungai Perlis KBG Major Major Major
Paka2 Major Major Major
Paka6 Major Major Major
Batu Gaja BG3 Major Traces Major Major
Tlaga Jatoh TJ Major Traces Major
Devonian Sanai DHBS1 Major Minor Traces Major Major
Chepor GMHA Major Major Major Traces
AJ1 Major Major Major Traces
Temah Tasoh TTJA9 Major Traces Major Major Traces
Silurian-Devonian Bendang Riang GR6 Major Major Minor Traces
Karak KP Major Major Major
BB1 Major Major Major
Ordovician-Devonian Balling BL5 Minor Minor Major Traces
Kroh PH1 Major Major Minor Traces
Cambrian Matchinchung M2 Major Traces Major Traces

below 10 ppm. When compared with other black shales from this study, concentrations of several trace elements including Mo, Cu, Pb, Zn, Ni, Se,
the Cambrian black shale sample shows low concentrations of all ele- Ba, and U when compared with other Palaeozoic black shales in Penin-
ments except for Sr due to the high carbonate content of this shale. sular Malaysia. Carboniferous black shales are enriched in As and Co rel-
Ordovician-Devonian black shales show the highest Cr contents ative to other black shales. Carboniferous-Permian black shales exhibit
among the studied black shales. Devonian black shales have the highest the highest V contents, while Permian black shales exhibit the highest
Ga and Rb contents among the analyzed samples.
Table 3
Correlation coefcients (r2) between trace elements and major ox-
Illite crystallinity (IC) of the Palaeozoic black shales from Peninsular Malaysia. ides have been calculated. Al2O3 exhibits strong positive correlations
with Sc, Ga, Rb, Ta, and Th and weak positive correlations with Hf and
Age Formation Sample Illite crystallinity (IC)
Nb. Fe2O3 has strong positive correlations with Zn, Ni, and Co. CaO
Permian Sri Jaya SJ2 0.38 shows weak positive correlations with Sr. K2O shows relatively strong
Bera BFM 0.27
positive correlations with Ga, Nb, Rb, Ta and Th. TiO2 shows strong pos-
Dohol DH2 0.32
Mersing MRS 0.38 itive correlations with Sc, Ga, Nb, Rb, Ta and Th as well as weak positive
Semanggol BK 0.46 correlations with Hf. P2O5 has a positive correlation with Ba.
Average 0.36
Carboniferous-Permian Kubang Pasu BC1 0.32
BC2 0.32 4.2.3. Rare earth elements
BC3 0.32 The distribution of rare earth elements (REE) in the Palaeozoic black
Kati bed KB3 0.27 shales from Peninsular Malaysia is shown in Table 6. Average sum of
KB5 0.46
Kenny Hill PUT2 0.32
rare earth elements (REE) ranges between 31 and 325 ppm. Samples
NIL3 0.32 from the Permian black shales show the highest REE (325 ppm),
Average 0.34 while the Cambrian black shales have the lowest REE value
Carboniferous Sungai Perlis KBG 0.38 (31 ppm). Carboniferous and Permian black shales show positive corre-
Paka2 0.32
lations between Al2O3 and REE. On the other hand, REE has no corre-
Paka6 0.32
Batu Gaja BG3 0.32 lations with Al2O3 in the rest of the black shales. REE in the studied black
Tlaga Jatoh TJ 0.32 shales are normalized to values for the UCC as reported by Taylor and
Average 0.34 Mclennan (1985) (Fig. 5). In comparison with the UCC, three enrich-
Devonian Sanai DHBS1 0.27 ment types of REE are generally identied (Seredin and Dai, 2012): L-
Chepor GMHA 0.32
AJ1 0.42
type (light-REE; LaN/LuN N 1), M-type (medium-REE; LaN/SmN b 1,
Temah Tasoh TTJA9 0.38 GdN/LuN N 1), and H-type (heavy REE; LaN/LuN b 1). Additionally, nor-
Average 0.35 mal type (N-type) of REE distribution patterns represent very weak or
Silurian-Devonian Bendang Riang GR6 0.32 no fractionation among the L-, M-, and H-REE. Accordingly, the majority
Karak KP 0.46
of the Palaeozoic black shales from Peninsular Malaysia are classied as
BB1 0.32
Average 0.37 H-type where LaN/LuN b 1 ranging from 0.34 to 0.71. Exceptions are one
Ordovician-Devonian Balling BL5 0.27 sample from the Permian black shales (Sri Jaya Formation), one sample
Kroh PH1 0.32 from the Carboniferous black shales (Telaga Jatoh Formation), one sam-
Average 0.30 ple from the Devonian black shales (Chepor Formation), two samples
Cambrian Matchinchung M2 0.27
from the Silurian-Devonian black shales (Bendang Riang and Karak
98 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105

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 SJ2 55.41 0.95 27.91 0.75 0.01 0.54 0.02 0.07 3.80 0.11 10.20 99.76 0.50 29.38 1.0
Bera BFM 64.74 0.62 20.59 0.54 0.01 0.58 0.01 0.18 5.40 0.01 7.10 99.82 0.32 33.21 2.3
Dohol DH2 58.67 0.98 26.78 0.53 0.01 0.33 0.02 0.70 5.16 0.03 6.60 99.78 0.46 27.33 0.9
Mersing MRS 63.84 0.91 22.27 0.52 0.01 0.34 0.01 0.59 5.25 0.06 5.90 99.70 0.35 24.47 2.4
Semanggol BK 72.34 0.86 15.52 0.88 0.01 0.73 0.01 0.06 3.33 0.02 6.10 99.84 0.21 18.05 1.4
Average 63.00 0.86 22.61 0.64 0.01 0.50 0.01 0.32 4.59 0.05 7.18 99.78 0.37 26.17 1.6
Carboniferous-Permian Kubang Pasu BC1 70.96 0.70 12.49 2.86 0.03 1.29 1.33 1.42 4.02 0.10 4.60 99.82 0.18 17.84 1.4
BC2 62.21 1.01 16.42 4.56 0.02 1.83 0.80 0.86 6.14 0.13 5.80 99.79 0.26 16.26 1.2
BC3 74.01 0.70 11.12 2.75 0.02 0.95 0.38 0.50 4.86 0.07 4.40 99.80 0.15 15.89 0.8
Kati bed KB3 74.69 0.60 7.93 1.09 0.02 0.83 0.03 0.02 1.94 0.12 12.40 99.69 0.11 13.22 5.2
KB5 60.78 0.95 16.54 2.49 0.02 0.91 0.03 0.02 2.27 0.10 15.50 99.68 0.27 17.41 5.9
Kenny Hill PUT2 79.66 0.51 8.42 0.31 0.01 0.59 0.01 0.05 2.65 0.04 7.10 99.35 0.11 16.51 4.1
NIL3 61.60 1.02 18.69 1.58 0.01 1.45 0.04 0.04 5.20 0.13 9.90 99.67 0.30 18.32 3.9
Average 69.13 0.78 13.09 2.23 0.02 1.12 0.37 0.42 3.87 0.10 8.53 99.69 0.20 16.69 3.2
Carboniferous Sungai Perlis KBG 69.91 0.81 18.66 0.82 0.01 0.40 0.01 0.18 4.56 0.02 4.50 99.85 0.27 23.04 2.5
Paka2 60.19 0.99 25.15 0.97 0.01 0.58 0.01 0.18 5.96 0.01 5.70 99.78 0.42 25.40 0.3
Paka6 72.44 0.70 17.51 0.48 0.01 0.16 0.01 0.27 2.88 0.01 5.40 99.85 0.24 25.01 0.3
Batu Gaja BG3 75.07 0.66 12.26 0.98 0.01 1.27 0.01 0.04 3.87 0.01 5.70 99.83 0.16 18.58 1.9
Tlaga Jatoh TJ 53.22 1.20 21.66 5.28 0.01 1.08 0.13 0.04 6.72 0.05 10.30 99.76 0.41 18.05 3.1
Average 66.17 0.87 19.05 1.71 0.01 0.70 0.03 0.14 4.80 0.02 6.32 99.81 0.30 21.84 1.6
Devonian Sanai DHBS1 51.42 0.78 15.17 4.79 0.03 1.63 6.86 0.06 5.28 0.17 13.50 99.74 0.30 19.45 4.9
Chepor GMHA 58.99 0.72 16.05 7.93 0.72 1.83 0.28 0.09 4.72 0.09 8.30 99.78 0.27 22.29 1.7
AJ1 53.00 0.93 21.30 7.99 0.25 2.62 0.06 0.07 5.85 0.05 7.60 99.77 0.40 22.90 1.1
Temah Tasoh TTJA9 76.96 0.23 5.21 2.12 0.01 0.28 0.08 0.03 1.47 0.42 12.70 99.50 0.07 22.65 6.9
Average 60.09 0.67 14.43 5.71 0.25 1.59 1.82 0.06 4.33 0.18 10.53 99.70 0.26 21.70 3.7
Silurian-Devonian Bendang Riang GR6 82.32 0.46 8.60 1.45 0.01 0.38 0.05 0.02 0.95 0.51 4.70 99.44 0.10 18.70 2.4
Karak KP 61.17 1.06 24.10 0.88 0.01 0.36 0.01 0.21 4.35 0.03 7.60 99.82 0.39 22.74 1.2
BB1 72.98 0.69 14.49 0.78 0.01 0.64 0.01 0.06 3.11 0.02 7.00 99.83 0.20 21.00 2
Average 72.16 0.74 15.73 1.04 0.01 0.46 0.02 0.10 2.80 0.19 6.43 99.70 0.23 21.35 1.9
Ordovician-Devonian Balling BL5 92.48 0.11 3.34 0.53 0.01 0.05 0.02 0.02 0.16 0.02 3.20 99.97 0.04 30.36 0.9
Kroh PH1 70.34 0.64 10.29 1.42 0.01 1.23 0.01 0.02 3.51 0.04 12.10 99.66 0.15 16.08 8.2
Average 81.41 0.38 6.82 0.98 0.01 0.64 0.02 0.02 1.84 0.03 7.65 99.82 0.09 18.17 4.6
Cambrian Matchinchung M2 8.31 0.09 1.64 0.50 0.01 1.07 47.6 0.01 0.69 0.01 39.90 99.90 0.20 18.22 0.5

formations) and one sample from the Ordovician-Devonian black shales
(Baling Formation). These exceptions are classied as L-type as LaN/
LuN N 1. In order to avoid interference of the Gd anomaly with the Eu
anomaly, the Eu anomaly is calculated as EuN/EuN* = EuN /
[(SmN 0.67) + (TbN 0.33)] (e.g. Bau and Dulski, 1996; Dai et al.,
2016). The Palaeozoic black shales from Peninsular Malaysia show pos-
itive Eu anomalies ranging from 1.57 to 2.64. Ce anomaly is calculated as
CeN/Ce* = 0.5LaN + 0.5PrN (Dai et al., 2016). With few exceptions, the
studied black shales exhibit positive Ce anomalies ranging from 1.18
to 3.58. The exceptions include the Permian Bera Formation, Carbonifer-
ous Sungai Perlis Formation, Ordovician-Devonian Baling Formation
and Cambrian Matchinchung Formation. These formations exhibit neg-
ative Ce anomalies ranging between 0.76 and 0.22.
4.2.4. Total organic carbon (TOC)
Total organic carbon (TOC) contents of the Palaeozoic black shales
from Peninsular Malaysia are shown in Table 4. They range between
0.3 and 8.2 wt.%. There is no trend in the distribution of TOC among
the analyzed shales with regard to their ages or localities. TOC contents
exhibit positive correlations with Pb, U and V (Fig. 6).
5. Discussion
5.1. Composition and weathering intensity of source rock(s)
Palaeozoic black shales are widely distributed in Peninsular Malaysia
and cover a range of different age intervals. Therefore, they could have
been sourced from different pre-existing source rocks. In addition,
there is no information about the nature of the Precambrian basement
rocks in Malaysia. Thus, this section attempts to examine the possible
source rocks(s) for the studied black shales and the degree of
weathering of these rocks as well as the nature of the basement rocks
in Malaysia. Many studies have shown that during uvial transport of
Al- and Ti-bearing detrital materials, Al and Ti endure insignicant frac-
tionation (e.g., Yamamoto et al., 1986). Hence, the Al2O3/TiO2 ratios of
sedimentary rocks should be similar to those of their magmatic source
rocks. In most igneous rocks, Al concentrates mostly in feldspars and
Ti in mac minerals (e.g. pyroxene, hornblende, biotite, ilmenite, and
magnetite). Therefore, the values of the Al/Ti ratio of igneous rocks
gradually increase with increasing SiO2 contents (Moosavirad et al.,
2011). Al2O3/TiO2 ratio and SiO2 contents vary in the igneous rocks as
follows: (a) Al2O3/TiO2 were 3 to 8 in mac igneous rocks (SiO2 content
from 45 to 52 wt.%), (b) Al2O3/TiO2 ratios were 8 to 21 in intermediate
igneous rocks (SiO2 content from 53 to 66 wt.%), and (c) Al2O3/TiO2 ra-
tios were 21 to 70 in felsic igneous rocks (SiO2 content from 66 to
76 wt.%) (e.g. He et al., 2010; Dai et al., 2015). The Al2O3/TiO2 ratios of
the studied black shales vary between 13 and 33 suggesting that the
source rocks of these shales range from intermediate to felsic in compo-
sition. According to Hayashi et al. (1997), the SiO2 content of most igne-
ous rocks can be evaluated from their Al2O3/TiO2 ratio by the following
equation:
SiO2(wt.%) = 39.34 + 1.2578(Al2O3/TiO2)-0.0109(Al2O3/TiO2)2.
Therefore, the silica content of the source rocks can be inferred from
the Al2O3/TiO2 ratios of siliciclastic rocks using the above equation. The
SiO2 contents of probable magmatic source rocks of the Palaeozoic
black shales in Peninsular Malaysia are estimated by substitution of
Al2O3/TiO2 ratios of the studied shales in the equation of Hayashi et al.
(1997). These values ranged from 54 to 69 wt.% (with an average of
61 wt.%), suggesting that the source rocks of the studied shales are in-
termediate to felsic igneous rocks. In the Zr (ppm) versus TiO2 (wt.%) bi-
variate discrimination diagram (McLennan et al., 1980), the Palaeozoic
black shales plot in the felsic to intermediate igneous eld with the ma-
jority of black shales plotting in the eld of felsic igneous rocks (Fig. 7A),
conrming the results of the SiO2 contents and Al2O3/TiO2 ratios. This
Table 5
Trace elements (ppm) of the Palaeozoic black shales from Peninsular Malaysia.

Age Formation Sample Mo Cu Pb Zn Ni As Cr Ba Co Ga Hf Nb Rb Sr Ta Th U V W Zr Y

Permian Sri Jaya SJ2 0.3 3.0 10.1 2 2.5 8.0 88.9 669 1.9 29.5 10.9 16.2 259.6 133.9 1.5 33.1 5.3 137 3.0 338.5 48.9
Bera BFM 0.3 5.0 57.5 10 1.7 2.7 47.9 850 2.4 25.0 6.2 12.0 222.6 37.8 1.0 17.5 4.2 126 2.0 207.2 20.6
Dohol DH2 0.1 2.0 13.4 1 0.4 0.7 88.9 783 1.2 34.8 8.1 28.3 277.8 88.2 2.2 29.4 4.0 124 4.9 276.5 49.9

H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105

Mersing MRS 0.2 13.3 22.1 1 0.2 1.1 95.8 960 0.3 30.0 10.4 28.4 293.7 115.7 2.4 35.8 8.4 304 5.8 354.3 61.1
Semanggol BK 2.6 40.4 23.2 2 2.4 9.4 82.1 406 4.4 20.3 5.9 19.6 140.1 40.6 1.6 16.4 3.8 134 2.6 227.0 26.9
Average 0.7 12.7 25.3 3.2 1.4 4.4 80.7 733 2.0 27.9 8.3 20.9 238.8 83.2 1.7 26.4 5.1 165 3.7 280.7 41.5
Carboniferous-Permian Kubang Pasu BC1 0.3 14.2 9.4 159 19.6 10.6 54.7 472 9.4 15.5 8.1 18.0 115.2 106.0 1.3 13.8 1.7 97 1.1 300.4 26.8
BC2 0.3 16.6 14.6 34 27.1 16.2 102.6 542 14.2 23.4 8.2 29.2 176.2 68.7 2.3 20.9 2.3 181 2.4 300.3 31.9
BC3 0.4 15.7 35.3 96 20.6 6.2 54.7 384 12.3 15.5 12.7 23.5 122.9 63.1 1.7 14.1 2.3 96 1.3 537.2 32.3
Kati bed KB3 8.9 70.9 25.5 10 22.6 7.5 191.6 342 2.9 16.9 4.9 19.8 127.4 150.1 1.3 15.4 13.4 900 2.7 210.1 60.5
KB5 21.8 86.5 27.9 16 22.7 20.3 253.2 315.0 1.9 25.4 6.3 25.2 153.1 106.7 1.9 18.3 11.9 919 3.4 264.5 43.9
Kenny Hill PUT2 7.9 1.1 13.5 1 0.6 1.1 246.3 1063 0.2 17.4 3.9 14.7 116.5 12.6 1.0 13.6 8.7 2631 2.9 195.7 57.8
NIL3 2.9 16.8 39.4 4 4.6 6.4 218.9 795 1.8 29.1 6.5 27.1 233.4 162.3 1.8 26.9 9.8 496 4.8 266.1 72.6
Average 6.1 31.7 23.7 45.7 16.8 9.8 160.3 559 6.1 20.5 7.2 22.5 149.2 95.6 1.6 17.6 7.2 760 2.7 296.3 46.5
Carboniferous Sungai Perlis KBG 0.1 1.1 2.8 1 0.1 0.5 68.4 564 0.6 23.7 7.3 17.7 191.8 70.9 1.4 17.3 3.8 150 4.0 269.0 11.5
Paka2 0.1 0.7 2.4 1 0.3 5.4 88.9 840 0.9 29.3 8.6 22.4 264.8 32.7 1.8 20.6 4.1 184 3.9 303.8 39.8
Paka6 0.4 1.6 2.9 1 0.3 3.2 41.1 529 1.6 21.8 9.6 19.7 176.9 46.3 1.7 27.4 4.2 69 3.6 334.6 33.0
Batu Gaja BG3 1.5 3.5 83.9 3 1.1 5.4 54.7 574 0.8 17.1 4.0 14.4 177.9 13.0 1.0 11.4 4.6 239 2.1 149.6 24.7
Tlaga Jatoh TJ 4.9 111.1 54.8 54 37.2 330.8 171.1 353 3.5 44.5 7.3 25.2 218.7 39.3 1.8 30.6 10.9 370 4.1 274.9 37.6
Average 1.4 23.6 29.4 12 7.8 69.1 84.8 572 1.5 27.3 7.4 19.9 206.0 40.4 1.5 21.5 5.5 202.4 3.5 266.4 29.3
Devonian Sanai DHBS1 20.3 73.9 38.0 115 98.9 54.2 136.8 377 13.6 19.3 5.0 17.1 159.6 105.2 1.3 22.1 13.5 458 1.9 192.7 36.8
Chepor GMHA 0.2 38.3 16.4 78 127.5 104.4 68.4 643 39.0 21.7 5.0 25.2 178.5 46.4 1.9 22.3 1.7 126 2.7 181.6 36.3
AJ1 30.6 42.2 35.0 154 75.1 44.7 116.3 447 28.8 27.0 3.8 24.2 207.3 41.2 1.8 33.9 4.3 179 2.5 139.3 26.6
Temah Tasoh TTJA9 36.1 34.9 180 20 23.8 15.4 75.3 3258 3.9 9.4 1.6 7.0 53.8 89.0 0.6 8.0 13.4 411 1.8 81.3 35.9
Average 21.8 47.3 67.3 91.8 81.3 54.7 99.2 1181 21.3 19.4 3.9 18.4 149.8 70.5 1.4 21.6 8.2 293.5 2.2 148.7 33.9
Silurian-Devonian Bendang Riang GR6 3.6 47.2 22.5 1 2.5 30.8 130.0 3426 0.7 13.1 3.0 10.9 99.6 399.5 0.8 13.1 6.4 286 4.8 126.7 57.4
Karak KP 0.1 0.7 4.4 1 0.4 1.6 130.0 724 1.0 27.3 8.3 20.5 233.0 63.4 1.7 21.6 4.5 173 3.2 293.5 18.3
BB1 3.0 20.1 58.6 1 2.4 11.5 95.8 626 2.4 20.7 3.3 17.5 162.2 18.9 1.4 16.8 4.5 234 2.0 128.0 27.2
Average 2.2 22.7 28.5 4.7 1.8 14.6 118.6 1592 1.4 20.4 4.9 16.3 164.9 160.6 1.3 17.2 5.1 231 3.3 182.7 34.3
Ordovician-Devonian Balling BL5 3.3 2.6 7.0 1 0.4 7.6 13.7 117 0.4 5.0 2.2 2.6 20.4 12.1 0.1 4.5 1.7 17 1.0 91.3 7.2
Kroh PH1 10.1 23.6 164 5 5.5 0.5 314.7 698 1.4 17.1 3.7 15.4 135.0 44.3 1.2 13.2 12.9 903 2.4 162.7 35.7
Average 6.7 13.1 85.3 3 3.0 4.1 164.2 407 0.9 11.1 3.0 9.0 77.7 28.2 0.7 8.9 7.3 460 1.7 127.0 21.5
Cambrian Matchinchung M2 0.4 1.9 3.8 2 2.5 2.8 13.7 51 2.0 2.7 0.5 2.0 17.2 458.9 0.2 2.3 1.0 8 0.5 20.6 5.3

99
100 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105

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 SJ2 112.9 229.3 24.15 81.8 13.33 1.77 11.28 1.62 9.36 1.7 4.81 0.75 4.81 0.81 498.39
Bera BFM 26.7 61.5 6.81 25.7 4.74 0.81 3.59 0.53 3.54 0.72 2.43 0.41 2.88 0.48 140.84
Dohol DH2 76.7 150.4 17.17 59.3 10.76 1.89 9.92 1.58 8.85 1.83 5.22 0.75 5.22 0.83 350.42
Mersing MRS 85.1 162.1 18.7 68.8 12.06 2.21 12.38 1.93 10.9 2.15 6.27 0.96 6.24 0.95 390.75
Semanggol BK 48.7 120.8 11.05 39.1 6.9 1.32 6.03 0.86 5.02 0.91 2.61 0.42 2.71 0.41 246.84
Average 70.0 144.8 15.6 54.9 9.6 1.6 8.6 1.3 7.5 1.5 4.3 0.7 4.4 0.7 325.45
Carboniferous-Permian Kubang Pasu BC1 39.8 83.9 9.03 32.7 6.04 1.15 5.69 0.91 4.98 0.98 2.74 0.44 2.71 0.43 191.5
BC2 48.3 100.1 10.88 41.1 7.44 1.33 6.59 1.03 5.78 1.14 3.42 0.53 3.47 0.53 231.64
BC3 45.7 96.8 10.9 40.7 8.39 1.58 7.18 1.13 6.18 1.16 3.24 0.51 3.35 0.51 227.33
Kati bed KB3 68 116.8 16.01 62.3 12.01 2.42 12.49 1.79 10.47 2.03 6.09 0.91 6.02 0.96 318.3
KB5 54.3 96.3 12 43.6 7.75 1.41 6.99 1.09 6.69 1.44 4.62 0.72 5.18 0.84 242.93
Kenny Hill PUT2 38.7 66.6 8.03 27.8 5.13 0.82 6 1.04 6.58 1.53 4.86 0.73 4.96 0.85 173.63
NIL3 87.9 165.1 19.77 74 14.52 2.97 14.13 2.23 12.46 2.38 6.67 1 6.35 0.94 410.42
Average 54.7 103.7 12.4 46.0 8.8 1.7 8.4 1.3 7.6 1.5 4.5 0.7 4.6 0.7 256.54
Carboniferous Sungai Perlis KBG 20 22.6 2.59 6.8 1.01 0.24 1.18 0.23 1.65 0.38 1.55 0.27 2.21 0.39 61.1
Paka2 62.3 121.4 14.12 50.7 8.76 1.63 7.68 1.17 7.16 1.45 4.29 0.67 4.52 0.72 286.57
Paka6 26.4 44.5 4.52 15.7 2.75 0.5 3.81 0.73 4.51 1.05 3.23 0.53 3.55 0.59 112.37
Batu Gaja BG3 45.2 83.6 10.03 37.2 6.38 1.24 5.65 0.8 4.36 0.8 2.44 0.38 2.47 0.42 200.97
Tlaga Jatoh TJ 78.1 149.5 16.1 57.7 7.86 1.04 5.97 0.93 5.64 1.16 3.77 0.57 3.57 0.56 332.47
Average 46.4 84.3 9.5 33.6 5.4 0.9 4.9 0.8 4.7 1.0 3.1 0.5 3.3 0.5 198.70
Devonian Sanai DHBS1 51.3 101.3 11.32 42.4 7.4 1.22 6.52 0.99 5.69 1.14 3.08 0.5 3.19 0.47 236.52
Chepor GMHA 39.3 93 9.09 37.3 8.52 1.74 8.74 1.29 6.62 1.22 3.51 0.53 3.26 0.5 214.62
AJ1 73.3 166 15.86 53.2 9.87 1.48 7.38 1.06 5.95 1.02 2.68 0.45 2.76 0.42 341.43
Temah Tasoh TTJA9 28.4 56 7.2 27.9 4.69 0.89 4.62 0.7 4.24 0.9 2.62 0.4 2.59 0.42 141.57
Average 48.1 104.1 10.9 40.2 7.6 1.3 6.8 1.0 5.6 1.1 3.0 0.5 3.0 0.5 233.54
Silurian-Devonian Bendang Riang GR6 109 134.6 21.16 77.3 14.62 2.93 12.6 1.88 10.47 1.85 4.96 0.65 4.05 0.53 396.6
Karak KP 38.5 79.3 7.66 26.8 4.34 0.78 3.42 0.53 3.15 0.61 2.14 0.37 2.86 0.5 170.96
BB1 53.9 111.7 11.54 40.1 7.09 1.34 6.32 0.88 4.61 0.85 2.4 0.37 2.56 0.38 244.04
Average 67.1 108.5 13.5 48.1 8.7 1.7 7.4 1.1 6.1 1.1 3.2 0.5 3.2 0.5 270.53
Ordovician-Devonian Balling BL5 14.8 18.3 2.71 9.5 1.83 0.35 1.85 0.28 1.43 0.24 0.55 0.1 0.51 0.08 52.53
Kroh PH1 45.1 72.2 8.53 30.2 4.67 0.82 4.55 0.73 4.86 1.08 3.54 0.61 4.31 0.71 181.91
Average 30.0 45.3 5.6 19.9 3.3 0.6 3.2 0.5 3.1 0.7 2.0 0.4 2.4 0.4 117.22
Cambrian Matchinchung M2 6.7 12.9 1.51 5.6 0.99 0.23 1.12 0.18 0.99 0.18 0.47 0.08 0.47 0.07 31.49

Age Formation Sample LaN/LuN LaN/SmN GdN/LuN Ce/Ce*N Eu/Eu*N

Permian Sri Jaya SJ2 1.07 1.27 0.84 2.33 1.07

Bera BFM 0.43 0.84 0.45 1.77 0.43
Dohol DH2 0.71 1.07 0.72 2.31 0.71
Mersing MRS 0.69 1.06 0.79 2.49 0.69
Semanggol BK 0.91 1.06 0.89 1.94 0.91
Average 0.76 1.06 0.74 2.16 0.76
Carboniferous-Permian Kubang Pasu BC1 0.71 0.99 0.80 1.96 0.71
BC2 0.70 0.97 0.75 2.02 0.70
BC3 0.69 0.82 0.85 2.08 0.69
Kati bed KB3 0.54 0.85 0.79 2.42 0.54
KB5 0.50 1.05 0.50 2.05 0.50
Kenny Hill PUT2 0.35 1.13 0.43 2.03 0.35
NIL3 0.72 0.91 0.91 2.64 0.72
Average 0.60 0.96 0.72 2.17 0.60
Carboniferous Sungai Perlis KBG 0.39 2.97 0.18 1.61 0.39
Paka2 0.66 1.07 0.65 2.10 0.66
Paka6 0.34 1.44 0.39 1.87 0.34
Batu Gaja BG3 0.83 1.06 0.81 1.91 0.83
Tlaga Jatoh TJ 1.07 1.49 0.65 1.97 1.07
Average 0.66 1.61 0.54 1.89 0.66
Devonian Sanai DHBS1 0.84 1.04 0.84 2.00 0.84
Chepor GMHA 0.60 0.69 1.06 2.16 0.60
AJ1 1.34 1.11 1.06 2.04 1.34
Temah Tasoh TTJA9 0.52 0.91 0.67 1.85 0.52
Average 0.82 0.94 0.91 2.01 0.82
Silurian-Devonian Bendang Riang GR6 1.58 1.12 1.44 2.46 1.58
Karak KP 0.59 1.33 0.41 1.77 0.59
BB1 1.09 1.14 1.01 1.95 1.09
Average 1.08 1.20 0.95 2.06 1.08
Ordovician-Devonian Balling BL5 1.42 1.21 1.40 1.64 1.42
Kroh PH1 0.49 1.45 0.39 1.87 0.49
Average 0.95 1.33 0.89 1.75 0.95
Cambrian Matchinchung M2 0.73 1.02 0.97 1.59 0.73

indicates that the hidden basement rocks in Malaysia are dominated by between ages but also between localities of the same age. If the studied
felsic igneous rocks along with subordinate intermediate igneous rocks. black shales were derived from the same source, they would exhibit
The Zr-TiO2 binary plot, SiO2 contents Al2O3/TiO2 ratios and UCC- similar geochemical characteristics. These variations, therefore, suggest
normalized REE patterns show variations among the studied black shales a local provenance nearby the depositional basins of each black shales.
 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105 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.

Chemical weathering of the source rocks affects the composition of
siliciclastic sediments. The intensity of the chemical weathering is con-
trolled by various factors: the source rock composition, climatic condi-
tions, duration of weathering, and rates of tectonic uplift of source
region (e.g., Akarish and El-Gohary, 2008; Moosavirad et al., 2011).
Dai et al. (2013) used the Al2O3/SiO2 ratio to indicate the degree of
weathering of the sediment-source rocks. This ratio increases with in-
creasing the weathering intensity and thus can be used to evaluate the
climate conditions as well. The Al2O3/SiO2 ratios in the Palaeozoic
black shales from Peninsular Malaysia vary from one age to the other
ranging between 0.09 and 0.37. Ordovician-Devonian black shales
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 relative-
ly wet conditions during the Cambrian to relatively dry conditions dur-
ing the Ordovician followed by relatively wet conditions extends from
the Silurian to the Carboniferous, which followed by relatively dry con-
ditions during the formation of Carboniferous-Permian black shales and
nally to relatively wet conditions during the Permian (Fig. 7B).
102 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105

5.2. Depositional environment of black shales

Palaeo-redox conditions during sedimentation of siliciclastic rocks

Fig. 6. Positive correlations between TOC and Pb, U and V in the Palaeozoic black shales
from Peninsular Malaysia.
can be evaluated from their chemical analyses (e.g. Dypvik, 1984; Dill,
1986; Jones and Manning, 1994). In oxic environments, vanadium oc-
curs as V5+ and under mildly reducing conditions it is present as V4+
and reduced further to V3+ under more strongly reducing conditions
(Tribovillard et al., 2006). Nickel forms soluble Ni2 + or NiCl+ ions in
oxic environments, while under moderately reducing conditions, nickel
is removed from sediments into the overlying waters. Under sulfate-
reducing conditions, nickel forms insoluble NiS within pyrite
(Tribovillard et al., 2006). Chromium is present mainly as Cr4+ in oxic
environments and is reduced to Cr3+ under anoxic conditions, which
may indicate increased Cr export to the sediment under reducing condi-
tions (Algeo and Maynard, 2004). Compared to Ni and Cr, V is more ef-
fectively xed in sediments containing organic matter in anoxic
environments. Therefore, variations in the V/(V + Ni) and V/(V + Cr)
ratios can be used to indicate oxygenation of the depositional environ-
ment, and higher V/(V + Ni) and V/(V + Cr) ratios indicate more
strongly reducing conditions (Zhou and Jiang, 2009). Pi et al. (2014)

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.
 H. Baioumy et al. / International Journal of Coal Geology 165 (2016) 90105
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 de-
position. V/Ni ratio has been widely used to determine the degree of an-
oxia 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 com-
plexes (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 re-
ducing 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 sug-
gested 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 ma-
rine organic matter, while a V/Ni ratio b1.9 indicates predominantly ter-
rigenous 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 glob-
ally 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 mat-
ter 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/low-
grade metamorphic zone (e.g. Frey, 1987; Rainer et al., 2002). The
103
smectite to illite transformation comprises three stages. Stage 1 (early
diagenesis) is characterized by the presence of discrete smectite. In
stage 2 (middle diagenesis) smectite disappears and illite-smectite
mixed layer minerals (I/S) are formed. In stage 3 (late diagenesis) the
mixed layer peak merges with the illite peak resulting in the formation
of diagenetic illite. The late diagenesis illite has IC N 0.422, while the
anchizone is dened by the limiting values of 0.42 and 0.252 (Kubler
and Jaboyedoff, 2000). According to Dellisanti and Pini (2010), over-
mature rocks are characterized by a long-range ordered I\\S with an il-
lite content N 85% and KI in the range 0.650.45 (2). Based on the
abundance of illite (N85%) and IC values (27462), the majority of
the studied Palaeozoic black shales in Peninsular Malaysia are probably
anchimetamorphic and over-matured.
It is worth to mention that a lag in the relation between organic ma-
turity and clay mineral diagenesis has been reported (e.g. Rainer et al.,
2002) as a result of delay of clay mineral diagenesis. A lag in clay mineral
diagenesis has been noted in tuffs (Frey, 1987; Merriman and Peacor,
1999), in bitumen-rich rocks (Krumm, 1996) and in areas with abnor-
mally high geothermal gradients (e.g. near igneous intrusions; Kisch,
1991). Rainer et al. (2002) attributed the delay of clay mineral diagene-
sis to factors other than temperature. This means that the vitrinite re-
ectance of the studied black shales should be investigated to conrm
their maturity based on IC.
6. Conclusions
The Palaeozoic black shales of Peninsular Malaysia have been classi-
ed in this study into seven categories based on their age. These are the
Cambrian-Ordovician, Ordovician-Devonian, Silurian-Devonian, Devo-
nian, Carboniferous, Carboniferous-Permian and Permian black shales.
REE patterns, Eu anomalies, as well as Zr-TiO2 bivariate diagram indicate
mixed felsic and intermediate igneous source rocks for the studied black
shales. This indicates that the hidden basement rocks in Malaysia are
dominated by felsic igneous rocks. Mineralogical and geochemical vari-
ations among the studied shales (clay minerals, Al2O3/TiO2 ratios, SiO2
contents and UCC-normalized REE patterns) suggests local provenance
for each locality rather than regional and common source rocks for all
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 con-
ditions during the Cambrian to relatively dry conditions during the
Ordovician followed by relatively wet conditions extends from the Silu-
rian 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. Geochemical proxies
such as V/(V + Ni), V/(V + Cr) and V/Ni ratios as well as positive Ce
anomalies suggest reducing marine depositional environment for the
black shales and solely marine source input for the contained organic
matter. The relatively high concentrations of redox-sensitive elements
in the Devonian black shales may suggest the possible existence of De-
vonian anoxia and the Devonian-Carboniferous (D-C) boundary in
Malaysia. Abundance of illite and low IC values indicate that the major-
ity of the studied Palaeozoic black shales in Peninsular Malaysia are
anchimetamorphic and over-matured.
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