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Provenance, weathering, and paleoenvironment of the Upper Cretaceous

Duwi black shales, Aswan Governorate, Egypt

Article  in  Arabian Journal of Geosciences · April 2018

DOI: 10.1007/s12517-018-3500-z

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Provenance, weathering, and
paleoenvironment of the Upper Cretaceous
Duwi black shales, Aswan Governorate,
Egypt

Samir M. Zaid, Oussama A. EL-

Badry, Adel M. Akarish & Mahmoud
A. Mohamed

Arabian Journal of Geosciences

ISSN 1866-7511
Volume 11
Number 7

Arab J Geosci (2018) 11:1-17

DOI 10.1007/s12517-018-3500-z

1 23
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 Author's personal copy
Arabian Journal of Geosciences (2018) 11:147
https://doi.org/10.1007/s12517-018-3500-z

ORIGINAL PAPER

Provenance, weathering, and paleoenvironment of the Upper

Cretaceous Duwi black shales, Aswan Governorate, Egypt
Samir M. Zaid 1 & Oussama A. EL-Badry 1 & Adel M. Akarish 2 & Mahmoud A. Mohamed 1

Received: 6 October 2017 / Accepted: 15 March 2018

# Saudi Society for Geosciences 2018

Abstract
The mineralogy and geochemistry of the Upper Cretaceous Duwi black shales of Nile Valley district, Aswan Governorate, Egypt,
have been investigated to identify the source rock characteristics, paleoweathering, and paleoenvironment of the source area. The
Duwi Formation consists mainly of phosphorite and black shales and is subdivided into three members. The lower and upper
members composed mainly of phosphorite beds intercalated with thin lenses of gray shales, while the middle member is mainly
composed of gray shale, cracked, and filled with gypsum. Mineralogically, the Duwi black shales consist mainly of smectite and
kaolinite. The non-clay minerals are dominated by quartz, calcite, phosphate, dolomite, feldspar, with little gypsum, anhydrite,
iron oxides, and pyrite. Based on the CIA, PIA, and CIW values (average = 84, 94, 95, respectively), it can be concluded that the
litho-components of the studied shales were subjected to intense chemical weathering and reflect warm/humid climatic condi-
tions in the depositional basin. The provenance discrimination diagram indicates that the nature of the source rocks probably was
mainly intermediate and mafic igneous sources with subordinate recycled sedimentary rocks (Nubia Formation). Geochemical
characteristics indicate that the Duwi black shales in Nile Valley district were deposited under anoxic reducing marine
environments.

Keywords Provenance . Black shales . Upper Cretaceous . Aswan

Introduction other minerals. The organic fraction is mainly an insoluble

solid material (kerogen) which is entirely comparable to the
The black shales have attracted the interest of many re- organic matter present in many petroleum source rocks. The
searchers primarily because of their economic importance in abundance of organic rich layers was confirmed in place be-
terms of hydrocarbon development potential (i.e., source cause parts of the Duwi mine are still burning after they caught
rocks) as well as metal concentrations (Wignall 1993; El fire some years ago. The organic matter is derived from dom-
Kammar 1993; Armstrong-Altrin et al. 2013). Several black inating marine organisms under strong reducing conditions
shales are particularly metalliferous, mostly enriched in U, V, (El Kammar et al. 1990; El Kammar 1993).
Cu, Ni, and Zn (Schultz 1991). The black shale could be used The black shales in Egypt belong to two stratigraphic for-
also as an energy donator in an electric power plant and/or in mations namely Duwi at the base overlain by the Dakhla of
production of cement. The composition of the inorganic frac- Campanian–Maastrichtian age. Both formations persistently
tion may vary from a shale where clay minerals are predom- extend along the southern escarpments which bound the
inant, to carbonates with subordinate amounts of clay and Western Desert from Dakhla to Kharga Oasis, to south
Kharga at Sinn El-Kaddab escarpment, further to the western
reaches of Kom-Ombo, then traced northward along the Nile
* Samir M. Zaid Valley from Idfu to wadi Qena and the Galala plateau, as well
[email protected] as along the Red Sea Coast between Quseir and Safaga
forming a thick belt.
1
Department of Geology, Faculty of Sciences, Zagazig University, Black shales are argillaceous sediments containing high
Zagazig, Egypt percent of total organic carbon. Their depositional controls
2
Department of Geological Sciences, National Research Centre, are not clear, but are widely viewed as a complex interplay
Dokki, Giza, Egypt between surface water productivity, rates of oxidation of
 Author's personal copy
147 Page 2 of 17 Arab J Geosci (2018) 11:147

organic matter, and/or dilution by non-organic material plain through Aswan at Nile Valley. The study area contains
(Bottcher et al. 2006). The mineralogy and chemistry of black occurrences of extensive black shale beds of Duwi Formation
shales have been affected, therefore by numerous factors in- (Late Campanian–Early Maastrichtian) that overlie a fluvial
cluding composition of source material, duration of variegated shale sequence in Quseir member of the older
weathering, transportation mechanisms, bulk sediment accu- Nubia Formation, with an undulating erosion contact (El-
mulation rate, prevailing organisms, chemical composition of Azabi and Farouk 2010). The entire succession is conform-
water, and diagenesis (Loukola-Ruskeeniemi 1991; Hayashi ably overlained by the deeper marine laminated gray to black
et al. 1997; Armstrong-Altrin et al. 2004, 2013). Shales that shales of the Dakhla Formation (Late Maastrichtian–Early
are the most abundant type of detrital sediments in sedimen- Paleocene) (Fig. 2).
tary basins (Pettijohn 1975) are represented by the average The Quseir shale member is composed of different var-
crustal composition of the provenance area much better than iegated shales, reddish brown, gray, and yellow in color.
any other siliciclastic sedimentary rocks (Nagarajan et al. The Duwi Formation composes of a lower phosphorite
2007), since they preserve the original signature of the source member represented by phosphorite bed intercalated with
rocks and diagenetic history (Mondal et al. 2012). Chemical thin lenses of gray shales of thickness ranging between
composition of the clastic sediments provides important infor- 0.2 and 0.6 m averaging 0.4 m, and the middle shale
mation on provenance, weathering conditions, and sediment member is mainly composed of gray shale, cracked, and
recycling (Basu et al. 2016; Borghesi et al. 2016; filled with gypsum. Meanwhile, the Upper Phosphorite
Campodonico et al. 2016; Selvaraj et al. 2016; Tawfik et al. Member is composed of thin phosphatic beds. The
2016; Tobia and Shangola 2016; Armstrong-Altrin et al. Dakhla Formation is composed of gray to black shale,
2015a, b). Also, the geochemical parameters have been used papery, cracked, and filled with gypsum and ferruginous
by various authors to interpret the paleoenvironment and stains. Obviously, the deposition represents an initial stage
paleooxygenation conditions of ancient shales (Nagarajan of the Late Cretaceous marine transgression in Egypt
et al. 2007; Abou El-Anwar et al. 2017). (Glenn and Arthur 1990; El-Azabi and Farouk 2010).
Significant contributions have been made by several stud- The northwestern margin of the Red Sea consists of
ies in relation to the regional geology, sedimentology, miner- Precambrian crystalline basement together with Mesozoic,
alogy, geochemistry, and economic potentiality of the Upper Cenozoic pre-rift sediment, and the late Oligocene–Miocene
Cretaceous Duwi black shales exposed at Western Desert dis- to recent syn-rift sediments (Said 1990). The pre-rifting (Late
trict, Nile Valley district, and the Red Sea coastal zone (Sediek Cretaceous–Middle Eocene) deposits of a 500–700 m thick
and Amer 2001; Ghandour et al. 2003; Ibrahim et al. 2004; occupy the troughs of synformal-like folds within the base-
Schulte et al. 2011, 2013; El Kammar 2014; Ghanem et al. ment hill ranges. The lower part of the pre-rift section is the
2016; Abou El-Anwar and Gomaa 2016; Abou El-Anwar 130-m massive thick-bedded siliciclastic Nubia Formation
et al. 2017). In contrast, no detailed studies that focused on which overlain by 220–370-m-thick sequence of interbedded
provenance, paleoweathering, and paleoenvironments of the shales, sandstones, and limestones of Quseir, Duwi, Dakhla,
Upper Cretaceous Duwi black shales have been documented. and Esna formations (Khalil and McClay 2009). The upper-
Therefore, the present work aims to examine the mineralogy most pre-rift strata consists of 130–200 m of competent, thick-
and geochemistry of the Upper Cretaceous Duwi black shales bedded limestones and cherty limestone of the lower to middle
at five sites at El-Nasr company open-pit exploited phosphate Eocene Thebes Formation. The marine upper Eocene and
mines, Nile Valley district (Kom-Mir, El Sebaiya, Um Oligocene deposits are absent, indicating that the region must
Salamah, Badr-3, Elgididh-6, Figs. 1 and 2) in Aswan have undergone elevation changes during these two epochs
Governorate, Egypt, to identify the source rock characteristics, (Said 1992). The late Oligocene to recent syn-rift strata un-
palaeoweathering, and paleoenvironment of the source area. conformably overlie Thebes Formation and vary in thickness
from less than 100 m on shore to as much a 5 km in offshore
basin (Heath et al. 1998). Faulting with a dominant NW trend
Geological setting is the main feature in the region and forms complicated horsts
and grabens with outcropping basement rocks covering the
The study area lies between longitudes 32° 30′–32° 50′ E and major part of this region.
latitudes 25° 05′–25° 30′ N, on the southwestern side of the
Nile Valley (Fig. 1). The stratigraphic succession is of Late
Campanian–Early Paleocene age and represents a part of the Samples and methodology
dominated sedimentary deposits of black and variegated
shales that are widely distributed in Upper Egypt. This suc- Twenty-five representative samples of Duwi black shale were
cession laterally extends from the New Valley in the Western collected from the Duwi phosphate mines belonging to El
Desert to Safaga–El Qusier region on the Red Sea Coastal Nasr mining company namely Kom-Mir, El Sebaiya, Um
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Arab J Geosci (2018) 11:147 Page 3 of 17 147

Fig. 1 Geological map of the study area showing locations of studied sites (modified after Conoco 1987)

Salamah, Badr-3, and Elgididh in Aswan Governorate, Nile Twenty-five shale samples were grinded to < 63 μm
Valley district (Fig. 1). The petrographic characteristics of and dried at 110 °C and treated with lithium metaborate
10 selected samples were investigated by thin section mi- and tetraborate to make pressed powder pellets. They
croscopic observations. The mineralogy of all Duwi black were analyzed using X-ray fluorescence Pnalytical
shale samples was determined by X-ray diffraction (XRD) Axios Advanced XRF equipment for major and trace
analysis using both smear-on glass slide and powder press element geochemistry. XRF analyses were performed at
techniques (Hardy and Tucker 1988). The analysis was the laboratory of the Central Metallurgical Research and
done by a Philips X-ray diffractometer model PW/1710 Development Institute, Egypt. The accuracy of the ana-
(CuKα radiation with 40 kV, 35 mA, and 2°–70° 2-theta). lytical method was evaluated using the standard MESS-3
Clay minerals were identified by their characteristic re- and was 100 ± 3% for all oxides and trace elements. Loss
flections (Moore and Reynolds Jr 1997). Also, the samples on ignition (LOI) was estimated by heating sample at
were scanned by scanning electronic microscope (SEM, 1000 °C for 2 h. Major element data were recalculated
3.5 nm of resolution) equipped with energy-dispersive spec- to an anhydrous (LOI-free) basis and adjusted to 100%
trometer (EDS), to determine the chemical composition during before using them in various diagrams. The total iron is
SEM observations. XRD and SEM-EDS analyses were per- expressed as Fe2O3. The correlation coefficient has been
formed at the laboratory of the Central Metallurgical carried out for the chemical data by using the Davis
Research and Development Institute, Egypt. method (1986).
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147 Page 4 of 17 Arab J Geosci (2018) 11:147

Fig. 2 Correlation chart of the Duwi Formation at the studied locations: (1) Kom-Mir, (2) El Sebaiya, (3) Um Salamah, (4) Badr-3, and (5) Elgididh-6,
Aswan Governorate, Egypt

Results Mineralogy

Petrography The XRD results indicate that the Upper Cretaceous Duwi
black shales consist mainly of quartz, calcite, smectite and
The shales consist mainly of foraminiferal argillaceous matrix kaolinite clay minerals, phosphate, dolomite, feldspar, with
(Fig. 3a). In some samples, the argillaceous matrix is color- little gypsum, anhydrite, iron oxides, and pyrite (Table 1;
laminated (Fig. 3b). This lamination resulted from the alter- Fig. 4). Iron oxides (mainly hematite) are recorded in
ation of organic matter-rich and iron oxide-rich laminae. Sebaiya, Badr-3, and Elgididh-6 black shales (Table 1). It
Sand-sized grains (average 31%, Table 1) are embedded in increases from east to west. Smectite and kaolinite (average
argillaceous materials (Fig. 3c, d). Quartz grains are generally = 20.48%) constitutes the most abundant clay minerals. Their
fine to very fine, angular to subangular, monocrystalline, values increase from the west (Badr-3, Elgididh-6, and Um
poorly sorted, and exhibit either uniform or undulose extinc- Salamah) to the east (Sebaiya). The bulk rock mineralogy of
tion (Fig. 3c, d). Feldspars (average 4%, Table 1) are repre- the shales indicates the presence of phyllosilicates with abun-
sented mainly by Na-plagioclase (albite) and K-feldspar (mi- dant quartz, calcite, phosphate (fluorapatite), dolomite, and
crocline). Iron oxides (average 1%, Table 1), are formed of feldspar. Quartz is the most abundant non-clay minerals (av-
very fine material or dark patches replacing the clay matrix erage = 31%) followed by calcite (average = 20.9%),
(Fig. 3e). This indicates that these iron oxides are authigenic fluorapatite (average = 10.4%), dolomite (average = 6.9%),
and were either precipitated by moving fluids or resulted by feldspar (average = 4%), gypsum (up to 3.5%), anhydrite (up
the degradation and breakdown of iron-rich minerals and de- to 1.5%), iron oxide, and pyrite (up to 1.5%). The mineralog-
trital ferromagnesian silicates. ical composition indicates a high MMI (mudrock maturity
 Author's personal copy
Arab J Geosci (2018) 11:147 Page 5 of 17 147

Fig. 3 Photomicrograph and SEM of the Duwi black shales showing a pyramidal syntaxial overgrowth (QO); d feldspar grains embedded in
highly foraminiferal argillaceous matrix with thin bands of gypsum/ calcite (Ca) cement and argillaceous matrix (note feldspar overgrowth
anhydrite (G), a laminated foraminiferal shale (note minor scattered silt- (FO)); e argillaceous matrix are partially replaced by iron oxides (I); f
sized quartz grains (Q) in argillaceous matrix); b fine to very fine quartz detrital particles of smectite (Sm); g detrital platelets of kaolinite (K) (note
grain (Q) embedded in argillaceous matrix (note rhombic dolomite irregular edges of smectite (Sm); and h detrital particles of smectite (Sm)
crystals (D) and aggregates of framboidal pyrite (Py); c quartz grains and kaolinite (K) embedded in calcite (Ca) cement
(Q) embedded in argillaceous matrix (note pore-filling euhedral

index; MMI = 100 × phyllosilicates / (phyllosilicates + were carried by fluvial action, which finally interfered and
quartz + feldspars; Bhatia 1985), with an average value of 36 admixed with marine environments (marginal marine, low
(Table 1). energy, and reducing conditions of Duwi Formation)
(Hendriks et al. 1990).
Clay minerals Kaolinite (Fig. 3h, i) constitutes the second dominant clay
mineral in the studied black shale of Duwi Formation. It
Smectite (Fig. 3c–e, g–i) constitute the dominant clay mineral ranges from 0.2 to 1.3% (Table 1). Kaolinite in the marine
content of the studied shale samples. It ranges from 0.8 to deposits of Upper Cretaceous age are products of terrestrial
63.7% (Table 1). The abundance of smectite, the low content weathering and represent continental products of a warm and
of kaolinite, the presence of pyrite rhombs, and the complete at least seasonally humid climate, being eroded and
absence of illite in the shales refer to a deposition under fluvio- transported toward the sea by rivers (Hendriks et al. 1990;
marine environment under alkaline-reducing conditions Hallam et al. 1991). In addition to a detrital origin, smectite
(Sediek and Amer 2001). Also, the absence of any volcanic and kaolinite may also develop by diagenetic processes due to
precursor, such as tuff or glass in the studied shales, proves the circulation of acid solutions (Ghandour et al. 2003).
that smectite is mainly of detrital origin. Generally, the clay
mineral associations in the studied shales with its smectite
dominance and low kaolinite suggest a terrestrial prove- Non-clay minerals
nance that are degraded from chlorite and illite after de-
position and had not attained intensive weathering, under Quartz (avg. = 31%, Table 1) was present as an important non-
a warm and semi-arid climate, and the resulted materials clay mineral in shales. Quartz grains (Fig. 3c, d) are fine to
 Author's personal copy
147 Page 6 of 17 Arab J Geosci (2018) 11:147

very fine grained, angular to subangular, mostly monocrystal-

Statistical parameters

Max

81.8
69
64
30
94
76
13

15
45

65

98
19
4
line, with normal and undulose extinction.
Carbonate minerals detected are calcite and dolomite.

4.87
Min

81
Calcite (Fig. 3e, i) was recorded in all studied sites except El

0
1
0
0
0
0

0
0
0
1

2
Sebaiya (Table 1). It ranges from 0.0% to about 94%. On the

10.4

36.0
31.1

20.9

0.32
20.5

91.0
4.0

6.9
1.4

1.1
3.4

8.9
Av

other hand, dolomite (Fig. 3c) was recorded only in shales of

Kom-Mir and Elgididh-6 phosphate mines. It reaches up to

43.2
Eg5
50

41

92
0
4
0
0
0

5
0
0

8
76% (Table 1). The presence of calcite and dolomite in

10.0
Eg4

40 shales in addition to the presence of foraminifers’ fossils

50

94
9
0
0

0
0
0
1

6
may indicate the deposition of this formation in a ma-

38.7
Eg3
19

68

12

93
rine environment.
0
0

0
0

0
0
1

7
Sulfates detected by XRD are gypsum and anhydrite
Elgididh-6

31.8
Eg2
30

56

14

91
0
0

0
0

0
0
0

9
34.1 (Table 1 and Fig. 3a). Anhydrite was found only in El
Eg1

Sebaiya black shale, while gypsum was recorded in all studied

29

56

15

94
0
0

0
0

0
0
0

6
sites except Elgididh-6 black shale. The anhydrite content
41.9
B5
18

61

13

95

reaches up to 13%, while gypsum content reaches up to

0
0

0
0

8
0
0

45%. The evaporites form from saline-rich fluids-brines.

25.0
B4

10
27

54

93
0

0
0

0
0
0
9

Brines may be generated by concentration of sea water, by

53.3

evaporation or freezing, or as residual connate fluids in the

B3
43

49

97
0
0
0
0
0

0
4
4

subsurface (Selley 1988).

6.7
B2
14

52

33

92
0
0

0
0

0
1

8
Badr-3

Anhydrite and gypsum was probably syn-precipitated

66.7
B1

under reducing conditions primarily as sulfides with

52

45

93
1
0
0
0
0

0
2

shale. After shale compaction, the sulfides oxidized to

US5

35.6
14
47

13

26

94

sulfates as a result of biogenic activity; the sulfates react

0

0
0

0
0
0

6
US4

25.0

with the calcic cement (produced by weathering of car-

30
15

50

86
14
0

0
0

0
0
0
5

bonate) to form gypsum. Due to the compaction of clays,

US3

67.0

the sulfates will be expelled and concentrated along the

32

65

91
0
0
0
0
0

0
1
2

9
Um Salamah

bedding planes as gypsiferous bands which can be seen in

US2

22.2
63
14

22

98

the field.
0
0
0
0

0
0
1

2
US1

17.0

Phosphate minerals encountered in Duwi black shales

64
19

17

95
0
0
0
0

0
0
0

are carbonate fluorapatite (francolite). It is recorded in

32.0
Sb5

all studied sites except El Sebaiya. It varies from 0 to

63

32

97

MMI = 100 × phyllosilicates / (phyllosilicates + quartz + feldspars) (Bhatia 1985)

0
5
0
0
0

0
0
0

3
Semi-quantitative mineralogical composition of bulk studied samples

69% (Table 1). The carbonate and phosphate minerals,

35.6
Sb4
41
15

13

31

86
14

Av average, Min minimum, Max maximum, MMI mudrock maturity index

0
0
0

0
0
0

in the shales, are indicating their deposition in a marine

17.0
Sb3

environment (Temraz 2005).

53
30

17

92
0
0
0
0

0
0
0

Feldspars detected by XRD are represented mainly by Na-

El Sebaiya

39.3
Sb2

10

35

85
44

15
11

plagioclase (albite) and K-feldspar (microcline) in the shales

0
0
0

0
0
0

(Fig. 4). It varies from 0 to 30% (Table 1). Microcline is

50.0
Sb1

10

15

37

89
33

11
0
4
0
0

1
0

relatively more common than plagioclase. The absence of

KM5

68.5

feldspar in most samples may indicate intensive degree of

46

37

88
12
17

0
0
0

0
0
0

chemical weathering.
KM4

81.8

Iron oxides detected by XRD in Duwi black shale samples

76

18

81
19
0
0
0

0
2
0
4

are represented mainly by hematite (Fig. 4). The hematite

KM3

37.0

content reaches up to 15% (Table 1). It is commonly present

69

10

87
13
17
0
4
0
0

0
0
0

as very fine material replacing the clay matrix or as dark

KM2

16.7

patches (Fig. 3f). Iron oxides can be formed either by pedo-

Kom-Mir

94

87
13
0
0

0
0

0
0
0
1
5

genic processes or by the precipitation of iron oxides from

KM1

4.9
45
14

86
14
39

laterally flowing surface or groundwater (Ollier and

0

0
0

0
0
0
2

Galloway 1990).
< 2 μm clay Sm
K

Pyrite spheres and framboids were recorded in most sam-

Clay minerals
Iron oxides

ples of the Duwi Formation except El Sebaiya black shale

Anhydrite
Location

Dolomite

F-apatite
Feldspar

Gypsum
Table 1

Calcite
Quartz

(Table 1 and Fig. 3c). It is recorded only in Um Salamah,

Pyrite

MMI

Badr-3, and Elgididh-6. The pyrite content reaches up to 4%

 Author's personal copy
Arab J Geosci (2018) 11:147 Page 7 of 17 147

Fig. 4 X-ray diffraction patterns of the Duwi black shale samples at (1) Kom-Mir (sample KM5), (2) El Sebaiya (sample Sb3), (3) Um Salamah (sample
US5), (4) Badr-3 (sample B2), and (5) Elgididh-6 (sample Eg5), Aswan Governorate, Egypt
 147
Page 8 of 17

Table 2 Major element composition (wt%) of Duwi black shales, Aswan Governorate, Egypt

Location Kom-Mir El Sebaiya Um Salamah Badr-3 Elgididh-6 Av Std

KM1 KM2 KM3 KM4 KM5 Sb1 Sb2 Sb3 Sb4 Sb5 US1 US2 US3 US4 US5 B1 B2 B3 B4 B5 Eg1 Eg2 Eg3 Eg4 Eg5

(SiO2)adj 52.99 52.65 54.80 53.36 55.31 52.25 52.13 54.15 54.25 53.69 54.46 52.44 53.91 54.39 54.02 53.55 51.85 52.75 55.55 55.70 51.08 52.01 53.95 54.02 52.83 53.47 1.43
SiO2 43.1 43.3 44.2 42.4 45.4 41.41 43.2 42.5 44.5 42.02 45.1 41.55 42.7 42.27 42.30 41.80 40.3 40.9 43.5 42.7 40.38 40.62 42.30 41.80 41.40 41.69 1.00
Al2O3 12.8 12.9 13.8 13.1 13.2 13.9 14.8 12.7 13.91 12.8 13.3 14.3 13.4 12.10 12.30 12.96 11.3 11.7 13.07 11.81 12.7 11.6 12.20 11.80 11.90 12.12 0.55
CaO 5.8 6.3 5.1 4.1 4.2 4.5 5.3 4.1 4.9 4.2 5.3 4.6 4.4 5.40 5.30 5.40 7.3 8.1 4.3 4.5 6.4 6.3 5.63 6.00 6.00 5.89 1.07
MgO 1.6 1.2 1.4 1.3 1.9 1.3 1.4 1.1 1.3 1.5 1.3 1.1 1.5 1.60 1.57 1.58 1.7 1.4 1.4 1.7 1.6 1.7 1.56 1.56 1.58 1.58 0.10
Fe2O3* 11.1 11.1 9.2 12.1 11.3 12.2 12 11.7 11.6 11.6 11.7 12.5 11.4 10.80 11.20 10.48 10.9 9.9 10.8 10.8 11.4 11.7 11.00 10.70 11.50 10.93 0.48
TiO2 0.9 1.3 0.9 1.1 1 1 0.9 0.91 1.1 1 0.96 0.45 0.27 0.57 0.55 0.56 0.4 0.4 0.7 0.6 0.5 0.4 0.55 0.53 0.54 0.53 0.09
P2O5 3.3 3.1 3.3 2.5 2.1 2.1 2 2.9 2.2 2.6 2.5 2.2 3.2 2.70 2.80 2.86 3.3 2.6 2.3 2.5 3.2 3.4 2.80 2.65 2.90 2.83 0.33
Na2O 0.9 0.9 0.8 0.8 0.9 0.88 1.1 0.8 0.86 0.8 0.8 0.8 0.7 0.60 0.60 0.66 0.7 0.7 0.6 0.5 0.8 0.6 0.63 0.62 0.70 0.64 0.08
K2O 1.7 2 1.8 1.9 1.9 1.8 2 1.6 1.5 1.6 1.7 1.6 1.5 1.53 1.54 1.60 1.7 1.7 1.5 1.4 1.9 1.6 1.59 1.57 1.70 1.61 0.13
SO3 0.14 0.14 0.15 0.16 0.19 0.17 0.17 0.17 0.16 0.14 0.15 0.13 0.14 0.14 0.15 0.16 0.13 0.13 0.14 0.15 0.17 0.18 0.14 0.15 0.15 0.15 0.02
LOI 18.66 17.76 19.35 20.54 17.91 20.74 17.13 21.52 17.97 21.74 17.19 20.77 20.79 22.29 21.69 21.94 22.27 22.47 21.69 23.34 20.95 21.9 21.60 22.62 21.63 22.03 0.61
Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.0 0.00
CaO* 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00
CIA 83.04 81.57 84.08 82.84 82.43 83.76 82.60 84.03 85.42 84.14 84.11 85.56 85.84 84.97 85.12 85.09 82.41 82.91 86.10 86.09 82.40 84.00 84.55 84.29 83.15 84.26 1.31
PIA 92.39 92.26 93.66 93.23 92.51 93.12 91.97 93.18 93.42 93.23 93.45 93.98 94.36 94.55 94.64 94.43 93.10 93.36 94.99 95.35 93.00 94.25 94.31 94.20 93.48 94.14 0.75
CIW 93.33 93.38 94.44 94.16 93.52 93.96 92.98 93.98 94.09 94.03 94.24 94.62 94.96 95.20 95.28 95.08 94.08 94.27 95.54 95.88 93.98 95.01 95.01 94.93 94.36 94.89 0.59
ICV 1.14 1.19 0.92 1.21 1.15 1.14 1.08 1.18 1.08 1.17 1.14 1.07 1.04 1.12 1.13 1.03 1.21 1.09 1.04 1.13 1.15 1.23 1.13 1.14 1.21 1.13 0.06
Al2O3/Na2O 14.22 14.33 17.25 16.38 14.67 15.80 13.45 15.88 16.17 16.00 16.63 17.88 19.14 20.17 20.50 19.64 16.14 16.71 21.78 23.62 15.88 19.33 19.37 19.03 17.00 18.86 7.28
Author's personal copy

K2O/Na2O 1.89 2.22 2.25 2.38 2.11 2.05 1.82 2.00 1.74 2.00 2.13 2.00 2.14 2.55 2.57 2.42 2.43 2.43 2.50 2.80 2.38 2.67 2.52 2.53 2.43 2.52 0.12
SiO2/Al2O3 7.43 6.87 8.67 10.34 10.81 9.20 8.15 10.37 9.08 10.00 8.51 9.03 9.70 7.83 7.98 7.74 5.52 5.05 10.12 9.49 6.31 6.45 7.51 6.97 6.90 7.32 1.47

(SiO2)adj = major element data were recalculated to anhydrous (LOI-free) basis and adjusted to 100%; Fe2O3* total Fe expressed as Fe2O3; CIA = [Al2O3 / (Al2O3 + CaO* + Na2O + K2O)] × 100 (Nesbitt
and Young 1982); PIA = [(Al2O3 − K2O) / (Al2O3 + CaO* + Na2O)] × 100 (Fedo et al. 1995); CIW = [Al2O3 / (Al2O3 + CaO* + Na2O)] × 100 (Harnois 1988); CaO* CaO in silicate phase. To calculate
CaO*, the assumption proposed by McLennan et al. (1993) was followed. ICV = (Fe2O3 + K2O + Na2O + CaO + MgO + MnO + TiO2) / Al2O3 (Cox et al. 1995)
n number, std standard deviation
Arab J Geosci (2018) 11:147
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Fig. 5 SEM and EDS spectrum

for the Duwi black shale samples.
a El Sebaiya (sample US1). b
Elgididh-6 (Eg5). Arrow mark
shows the points where the EDS
analyses were performed

(Table 1). The presence of pyrite in shales indicates the prev- Major and trace element concentrations
alence of a reducing environment during deposition. The re-
duction of sea water sulfate bacterial activity leads to pyrite The major element concentrations of the black shales of
formation in sediments (Berner 1982). the Upper Cretaceous Duwi Formation are reported in
Table 2. SiO2 is the dominant constituent of the Duwi
black shales in all studied sites (avg. = 41.69%, Table 2).
Al2O3 (avg. = 12.12%) and Fe2O3t (avg. = 10.93%) are the
second abundant elements in studied samples. The SiO2/
Al2O3 ratios vary from 5.05 and 10.8 (avg. = 7.32) higher
than that for pure kaolinite (1.18) and smectite (2.81–
3.31). This indicates that the shales consist mainly of a
mixture of smectite and kaolinite. Cao (avg. = 5.89%) and
P2O5 (avg. = 2.83%) are the third abundant elements in
shale samples (Table 2). The average values of Cao and
P2O 5 are relatively comparable to the average marine
black shales of Nile Valley (Temraz 2005). The shale
samples are less abundant in K 2O and MgO contents
and are depleted in Na2O, TiO2, and SO3. Depletion of
Na2O in shales suggests either lesser amount of plagio-
Fig. 6 Geochemical classification diagram using log (SiO2/Al2O3)–log clase detritus in the shales and/or comparatively intense
(Fe2O3/K2O) (after Herron 1988) chemical weathering at the source and during fluvial
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Table 3 Trace element composition (ppm) of the studied samples

Location Kom-Mir El Sebaiya Um Salamah Badr-3 Elgididh-6 Av Std

KM1 KM2 KM3 KM4 KM5 Sb1 Sb2 Sb3 Sb4 Sb5 US1 US2 US3 US4 US5 B1 B2 B3 B4 B5 Eg1 Eg2 Eg3 Eg4 Eg5

Sr 251 422 561 1597 277 1200 704 208 351 493 411 860 811.67 1025 660 953 129 644 891 1031 76 300 474 484 513 613 365
Ba 256 333 132 211 139 362 225 88 104 120 240 225 161 237 242 111 109 99 53 88 93 33 73 78 91 156 88
V 191 199 244 200 255 158 157 155 258 260 211 214 233 204 190 121 156 1452 209 412 111 144 377 3050 2677 474 766
Ni 29 39 31 35 38 32 31 32 29 32 30 35 25 32 31 30 30 147 38 60 81 48 126 188 154 55.3 46.3
Co 5 4 5 5 4 6 4 5 4 5 5 4 5 5 4 5 5 12 7 8 16 9 18 18 19 7.5 4.9
Cr 74 99 108 94 105 64 57 50 112 174 94 100 102 88 75 35 122 540 100 240 81 28 177 630 412 150 152
Zn 71 99 43 42 66 65 53 40 61 82 71 61 50 58 61 40 133 1041 121 63 69 36 1246 1600 1110 255 452
Cu 26 31 21 21 51 10 10 9 22 34 26 24 31 27 24 9 24 156 10 33 27 9 156 243 177 48 62
Zr 299 344 234 374 221 40 40 40 70 100 292 317 276 212 100 39 144 106 41 54 138 39 109 93 98 153 110
Cs 1.0 8.0 7.0 6.0 7.0 1.0 4.0 7.0 7.5 8.0 5.0 7.0 7.0 5.0 4.0 1.0 0.0 1.0 0.0 0.0 7.0 1.0 8.0 7.0 7.0 4.7 3.0
Cd 3.0 0.0 1.0 4.0 7.0 4.0 4.0 4.0 2.5 1.0 1.0 2.0 4.0 5.0 5.0 0.0 4.0 4.0 7.0 0.0 1.0 0.0 4.0 7.0 7.0 3.3 2.3
Mo 3.0 4.0 4.0 1.0 5.0 4.0 4.0 4.0 4.0 4.0 4.0 3.0 3.0 3.0 4.0 1.0 4.0 30.0 4.0 4.0 4.0 9.0 21.0 7.0 25.0 6.5 7.4
U 14.0 5.0 5.0 4.0 7.0 51.0 27.5 4.0 4.5 5.0 5.0 5.0 4.0 20.0 28.0 24.0 9.0 44.0 27.0 11.0 4.0 27.0 52.0 41.0 34.0 18.5 16.0
Th 18.0 10.0 10.0 9.0 14.0 1.0 5.0 9.0 9.5 10.0 10.0 10.0 11.0 8.0 5.0 1.0 10.0 9.0 1.0 10.0 9 1 8 9 8 8.2 4.0
Pb 14.0 63.0 15.0 13.0 12.0 14.0 13.5 13.0 13.5 14.0 31.0 30.0 13.0 13.0 13.0 13.0 12.0 30.0 15.0 13.0 14 15 33 20 29 19.2 11.5
Sc 7.0 5.0 7.0 8.0 5.0 9.0 10.5 12.0 9.5 7.0 6.0 7.0 7.0 7.0 8.0 11.0 10.0 7.5 6.6 8.5 8.0 12.0 13.0 8.0 9.0 8.3 2.1
Hf 1.2 1.4 1.5 1.2 1.4 1.2 1.2 1.3 1.3 1.3 1.6 1.7 1.3 1.5 1.3 2.0 1.8 1.7 1.2 1.6 1.0 1.2 1.6 1.3 1.5 1.4 0.2
Rb 28.0 29.0 44.0 41.0 46.0 9.0 9.5 10.0 22.5 35.0 34.0 38.0 60.0 48.0 38.0 10.0 33.0 41.0 10.0 19.0 28 10 32 31 30 29.4 14.1
La 24.6 26.5 7.3 25.4 11.2 30.0 18.6 14.3 30.2 16.3 9.6 17.2 0.1 10.3 3.0 19.1 34.3 0.2 20.6 6.0 17.7 21.9 8.7 10.4 8.2 8.3 2.1
Author's personal copy

Rb/Sr 0.11 0.07 0.08 0.03 0.17 0.01 0.01 0.05 0.06 0.07 0.08 0.04 0.07 0.05 0.06 0.01 0.26 0.06 0.01 0.02 0.37 0.03 0.07 0.06 0.06 0.1 0.1
Cr/Ni 2.55 2.54 3.48 2.69 2.76 2.00 1.84 1.56 3.86 5.44 3.13 2.86 4.08 2.75 2.42 1.17 4.07 3.67 2.63 4.00 1.00 0.58 1.40 3.35 2.68 2.7 1.1
La/Sc 3.51 5.29 1.04 3.18 2.23 3.33 1.77 1.19 3.18 2.33 3.51 3.51 0.01 1.47 0.38 1.74 3.43 0.03 3.12 0.71 2.21 3.51 3.51 1.29 0.91 8.3 2.1
La/Co 4.91 6.61 1.45 5.08 2.79 5.00 4.65 2.86 7.55 3.26 2.73 2.73 0.02 1.14 0.38 3.82 6.86 0.02 2.94 0.75 1.11 2.73 2.73 0.58 0.91 8.3 2.1
Th/Sc 2.57 2.00 1.43 1.13 2.80 0.11 0.48 0.75 1.00 1.43 1.67 1.43 1.57 1.14 0.63 0.09 1.00 1.20 0.15 1.18 1.13 0.08 0.62 1.13 0.89 1.1 0.7
Th/Co 3.60 2.50 2.00 1.80 3.50 0.17 1.25 1.80 2.38 2.00 2.00 2.50 2.20 1.60 1.25 0.20 2.00 0.75 0.14 1.25 0.56 0.11 0.44 0.50 0.42 1.5 1.0
Cr/Th 4.11 9.90 10.80 10.44 7.50 64.00 11.40 5.56 11.79 17.40 9.40 10.00 9.27 11.00 15.00 35.00 12.20 60.00 100.00 24.00 9.00 28.00 22.13 70.00 51.50 24.8 24.9
Ni/Co 5.80 9.75 6.20 7.00 9.50 5.33 7.75 6.40 7.25 6.40 6.00 8.75 5.00 6.40 7.75 6.00 6.00 12.25 5.43 7.50 5.06 5.33 7.00 10.44 8.11 7.1 1.8
V/Cr 2.58 2.01 2.26 2.13 2.43 2.47 2.75 3.10 2.30 1.49 2.24 2.14 2.28 2.32 2.53 3.46 1.28 2.69 2.09 1.72 1.37 5.14 2.13 4.84 6.50 2.7 1.2
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Fig. 7 Distribution of PAAS a 100.00

Kom-Mir
normalized abundance of Duwi El Sebaiya
black shales. a Major elements. b Um Salamah
Trace elements Badr-3

Sample/PAAS
10.00 Elgididh-6

1.00

0.10
SiO2 Al2O3 CaO MgO Fe2O3* TiO2 P2O5 Na2O K2O

Kom-Mir
b 10.00
El Sebaiya
Um Salamah
Badr-3
Sample/PAAS

Elgididh-6

1.00

0.10
Sr Ba V Ni Co Cr Zn Cu Zr Cs Cd Mo U Th Pb Sc Hf Rb

transportation of the detrital material of the shales. (average = 600 ppm). The high Sr content may be due to
Depletion of TiO2 and low K2O content indicates the the presence of aragonitic fossils and shells. Vanadium is
presence of relatively lesser quantities of phyllosilicate the second abundant trace element in black shale samples.
minerals in the shales (McCann 1991; Condie et al. The concentration of V (avg. = 376 ppm) is more than
1992; Armstrong-Altrin 2015). The SEM-EDS study re- those of Turekian and Wedepohl (1961) and Vine and
veals that the Duwi black shale samples are rich in Si, Tourtelot (1970) may be due to oxidation and
Al, K, and Fe contents, which may suggest the abun- weathering of the organic matter. Zinc is the third abun-
dance of quartz and clay minerals (Fig. 5). On the SiO2/ dant trace element in studied shales (255 ppm). The
Al2O3 versus Fe2O3/K2O geochemical classification dia- studied Duwi black shale samples also contain high
gram, the shale samples are classified mainly as Fe- concentrations of Cr, Ba, Zr, Cu, and Ni (158, 156,
shale (Fig. 6; Herron 1988), which is also consistent 153, 48, and 47 ppm, respectively). This enrichment is
with the petrographic data. due to the contribution by intermediate and mafic
The trace element concentrations of the Upper source rocks.
Cretaceous Duwi black shales for the five investigated The positive correlation between Al2O3 and SiO2,
sites are listed in Table 3. Figure 7a, b shows the distri- TiO2, and Zr (r = 0.59, 0.69, and 0.55, respectively, n
bution of major and selected trace element contents of the = 25, Table 4) can be explained by a terrigenous ori-
shales normalized to PAAS (Post Archaean Australian gin. This may be due to the presence of a considerable
Shale; Taylor and McLennan 1985). Compared to PAAS, amount of detrital clays. There is a weak positive cor-
the Upper Cretaceous Duwi black shales are highly relation between Fe 2O 3 and the SiO 2, Al 2O 3 , MgO,
enriched in SiO2, Al2O3, CaO, Fe2O3, P2O5, Sr, Ba, V, TiO2, Na2O (r = 0.18, 0.15, 0.17, 0.21, and 0.55, respec-
Ni, Cr, Zn, Cu, and Rb and slightly enriched in MgO, tively, Table 4) and a significant correlation between
K2O, U, Th, and Cd and Sc, Zr, Pb, and Co contents Fe2O3 and Ni (r = 0.82). This may be due to the asso-
and highly depleted in TiO2, Na2O, Hf, and Cs content. ciation of Fe3+ with clay minerals. K2O shows a posi-
The similar trace element content in shales may be related tive correlation with SiO2, Al2O3, and TiO2 (r = 0.51,
to the same source rock compositions. Strontium is the 0.30, and 0.49, respectively). This indicates the associ-
most abundant trace element in the studied samples ation of K2O with aluminosilicate phases.
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Table 4 Values of Pearson’s coefficient of correlation of major and trace elements in Duwi black shales

SiO2 Al2O3 CaO MgO Fe2O3 TiO2 P2O5 Na2O K2O Sr Ba V Ni Co Cr Zn Cu Zr Cs Cd Mo U Th Pb Sc Hf Rb

SiO2 1
Al2O3 0.599 1
CaO − 0.500 − 0.567 1
MgO − 0.116 − 0.450 0.226 1
Fe2O3 0.182 0.150 − 0.370 0.171 1
TiO2 0.621 0.687 − 0.403 − 0.393 0.211 1
P2O5 − 0.362 − 0.556 0.455 0.250 − 0.345 − 0.335 1
Na2O 0.353 0.478 − 0.131 − 0.368 0.552 0.649 − 0.284 1
K2O 0.519 0.307 0.179 − 0.123 0.206 0.491 − 0.039 0.748 1
Sr − 0.074 0.376 − 0.384 − 0.276 − 0.022 0.038 − 0.398 − 0.185 − 0.113 1
Ba 0.201 0.512 − 0.140 − 0.375 0.318 0.469 − 0.212 0.502 0.430 0.318 1
V − 0.254 − 0.296 0.378 0.126 − 0.288 − 0.278 0.018 − 0.223 − 0.069 − 0.087 − 0.285 1
Ni − 0.261 − 0.365 0.509 0.173 0.828 − 0.342 0.018 − 0.306 − 0.102 − 0.130 − 0.352 0.866 1
Co − 0.314 − 0.126 0.329 − 0.076 0.181 − 0.110 0.185 0.259 0.392 − 0.278 − 0.071 − 0.003 − 0.012 1
Cr − 0.235 − 0.309 0.427 0.141 − 0.453 − 0.319 − 0.049 − 0.340 − 0.181 − 0.047 − 0.372 0.855 0.980 − 0.095 1
Zn − 0.263 − 0.318 0.439 0.132 − 0.370 − 0.332 0.012 − 0.304 − 0.122 − 0.105 − 0.357 0.845 0.956 − 0.010 0.943 1
Cu − 0.214 − 0.311 0.415 0.189 − 0.372 − 0.312 0.008 − 0.286 0.156 − 0.132 − 0.335 0.892 0.974 − 0.037 0.960 0.982 1
Zr 0.300 0.553 − 0.069 − 0.217 0.750 0.253 0.169 0.276 0.351 0.087 0.504 − 0.159 − 0.152 − 0.022 − 0.176 − 0.204 − 0.126 1
Cs 0.290 0.244 − 0.280 − 0.266 0.128 0.277 − 0.030 0.264 0.182 − 0.236 0.002 0.158 0.139 0.096 0.131 0.180 0.241 0.356 1
Cd 0.048 − 0.042 − 0.062 0.216 − 0.071 − 0.153 − 0.302 − 0.121 − 0.065 0.051 − 0.108 0.501 0.395 − 0.020 0.392 0.464 0.476 − 0.154 0.028 1
Mo − 0.297 − 0.305 0.555 0.111 − 0.351 − 0.346 0.057 − 0.220 − 0.033 − 0.147 − 0.348 0.580 0.799 0.095 0.729 0.751 0.724 − 0.236 0.000 0.285 1
Author's personal copy

U − 0.358 − 0.123 0.333 0.156 − 0.216 − 0.311 − 0.176 − 0.271 − 0.110 0.202 − 0.062 0.446 0.561 0.004 0.543 0.661 0.571 − 0.521 − 0.340 0.432 0.605 1
Th 0.326 − 0.084 0.024 0.091 0.048 0.191 0.178 0.282 0.130 − 0.396 0.108 0.070 0.159 − 0.117 0.146 0.038 0.148 0.615 0.390 − 0.034 − 0.015 − 0.503 1
Pb 0.057 0.117 0.355 − 0.386 − 0.180 0.203 0.081 0.115 0.294 − 0.111 0.291 0.200 0.353 − 0.059 0.282 0.321 0.313 0.374 0.310 − 0.164 0.364 0.088 0.119 1
Sc − 0.429 − 0.416 0.121 0.038 0.154 − 0.289 0.144 − 0.180 − 0.215 − 0.047 − 0.419 − 0.024 0.041 − 0.035 0.029 0.194 0.068 − 0.623 − 0.181 − 0.064 0.222 0.395 − 0.446 − 0.245 1
Hf − 0.076 − 0.127 0.277 0.066 − 0.398 − 0.306 0.031 − 0.313 − 0.242 0.081 − 0.117 0.073 0.207 − 0.376 0.210 0.171 0.160 0.029 − 0.187 − 0.157 0.241 0.070 0.004 0.230 0.107 1
Rb 0.344 0.172 − 0.088 0.350 − 0.174 − 0.021 − 0.029 0.061 0.168 − 0.165 0.076 0.056 0.124 − 0.046 0.111 0.037 0.166 0.558 0.416 0.284 0.051 − 0.287 0.590 0.003 − 0.573 0.096 1
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et al. 2017). According to Fedo et al. (1995), the CIA,

CIW, and PIA values of ~ 60 indicates low weathering,
~ 60–80 moderate weathering, and more than 80 indicate
intensive weathering. The CIA values of the Upper
Cretaceous Duwi black shales varies from 82 to 86%
(avg. = 84%). The average CIA is higher than the PAAS
values (70–75; Taylor and McLennan 1985), suggesting
an intensive degree of chemical weathering in the source
area. The PIA values range from 92 to 95% (avg. = 94%)
indicating a high degree of alteration of source material.
CIW values range from 93 to 96% (avg. = 95%) also in-
dicate high degree of weathering. Based on CIA, PIA, and
CIW values (> 80%), it can be concluded that the litho-
components in shales were subjected to intense chemical
Fig. 8 Provenance discrimination diagram for shales (after Roser and weathering and reflect warm/humid climatic conditions in
Korsch 1988). Discriminant function 1 = (− 1.773 × TiO2%) + (0.607 × the depositional basin (McLennan et al. 1993).
Al2O3%) + (0.76 × Fe2O3T%) + (− 1.5 × MgO%) + (0.616 × CaO%) + The maturity of shale can be identified by the ratio values
(0.509 × Na2O%) + (− 1.22 × K2O%) + (− 9.09). Discriminant function of SiO2/Al2O3, Al2O3/Na2O, and K2O/Na2O, which increase
2 = (0.445 × TiO 2 %) + (0.07 × Al 2 O3%) + (− 0.25 × Fe 2 O 3 T%) + (−
1.142 × MgO%) + (0.438 × CaO%) + (0.432 × Na2O%) + (1.426 × K2O when maturity increases. The ratio values > 6, > 5, and < 0.5,
%) + (− 6.861) respectively, may indicate high maturity of sediments (Cox
et al. 1995). The SiO2/Al2O3, Al2O3/Na2O, and K2O/Na2O
ratio values of the Duwi black shales in all studied sites (~
Discussion 5.0–10.8, ~ 13.4–23.6, and ~ 1.7–2.8, respectively) suggest
moderate compositional maturity.
Source area weathering The index of compositional variability (ICV; Cox et al.
1995) is considered as an important parameter to evaluate
The intensity and duration of weathering in clastic sedi- the maturity of sediments (Cullers 2000). ICV values are high
ments can also be assessed by examining the relationship (> 1) for detrital ferromagnesian minerals and feldspars and
between alkali and alkaline earth elements (Nesbitt and low (< 1) for the clay minerals subjected to intensive
Young 1982). The degree of weathering is quantified by weathering processes (Cox et al. 1995; Cullers 2000). The
various methods. The commonly used weathering indices ICV values of the Duwi black shales range from 0.92 to
like chemical index of alteration (CIA; Nesbitt and Young 1.23% (average = 1.13 ± 0.06, n = 25) are slightly more than
1982), chemical index of weathering (CIW; Harnois 1 (Table 2), indicating the presence of detrital ferromagnesian
1988), and plagioclase index of alteration (PIA; Fedo minerals beside the abundant clay minerals. Compositionally
et al. 1995) are widely used to deduce the intensity of submature to mature sediments with slightly high ICV values
the source area weathering (Armstrong-Altrin and are partially recycle deposits derived by intensive weathering
Machain-Castillo 2016; Zaid 2017a, b; Abou El-Anwar of source rocks (Zaid 2017a, b).

Table 5 Range of elemental ratios of Duwi black shales in this study compared to the ratios in similar fractions derived from felsic, mafic rocks, and
upper continental crust

Elemental ratio Kom-Mira El Sebaiyaa Um Salamaha Badr-3a Elgididh-6a Range of sediment Range of sediment UCCc
from felsic sourcesb from mafic sourcesb

La/Sc 3.05 2.36 3.07 1.80 3.0 2.50–16.3 0.43–0.86 2.21

La/Co 2.21 2.34 2.21 2.76 2.21 1.80–13.8 0.14–0.38 1.76
Th/Sc 1.99 0.75 1.29 0.72 0.77 0.84–20.5 0.05–0.22 0.79
Th/Co 1.42 0.76 1.02 2.41 0.72 0.67–19.4 0.04–1.40 0.63
Cr /Th 8.55 22.03 10.93 46.24 41.13 4.00–15.0 25–500 7.76
a
This study
b
Cullers (1994, 2000), Cullers and Podkovyrov (2000)
c
Taylor and McLennan (1985)
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Fig. 9 Plot of V versus Al2O3 in

3500
the Duwi black shales for
paleoenvironmental 3000
Deep Marine
reconstructions 2500 environments

V (ppm)
2000

1500
1000
Shallow Marine and
500 Fluvial environments
0
0 2 4 6 8 10 12 14 16

Al2O3 (Wt%)

Provenance black shale are compared in Table 5, with those of sedi-

ments derived from mafic and felsic source rocks (Cullers
The chemical analyses of the clastic sediments has been wide- 1994, 2000; Cullers and Podkovyrov 2000; Taylor and
ly used to identify the source rock characteristics McLennan 1985). These ratios of the studied shale sam-
(Armstrong-Altrin et al. 2015a, b; Abou El-Anwar and ples fall within the range of sediments derived mainly
Gomaa 2016; Zaid 2017a, b). In order to infer the provenance from intermediate and mafic igneous source rocks
of siliclastic rocks, several major and trace element-based dis- (Table 5). The Precambrian gabbro and metagabbro–dio-
crimination diagrams have been proposed by many investiga- rite complex could have been the main source rocks with
tors (Roser and Korsch 1988; Floyd et al. 1989; McLennan subordinate recycled Upper Cretaceous Nubia Formation
et al. 1993; Verma and Armstrong-Altrin 2013, 2016; Verma for Duwi black shales.
et al. 2016). On the major element-based provenance discrim-
ination diagram of Roser and Korsch (1988), the studied Depositional environment
Upper Cretaceous Duwi black shales plot exclusively in the
quartzose sedimentary provenance fields (Fig. 8). The Al2O3/ The chemical analysis data can be used to evaluate the
TiO2 ratio and SiO2 contents can be used to identify the source paleo-redox conditions of siliciclastic rocks during sedimen-
rock (Hayashi et al. 1997). The Al2O3/TiO2 ratio of the Duwi tation (Armstrong-Altrin et al. 2015a; Armstrong-Altrin and
black shales vary from 9.92 to 49.6 (avg. 23.6), and SiO2adj Machain-Castillo 2016). The high enrichment of Sr, V, Ni, Cr,
contents vary from 51.0 to 55.7 wt% (avg. 53.47 wt%). These Zn, and Cd in the investigated Duwi black shale samples is
values suggest that the source rocks for the shales are inter- comparable with those values of modern black shales directly
mediate and mafic igneous rocks. K2O/Na2O ratio can be due to mafic input. The average value of Fe2O3/TiO2 ratio is
considered as a simplified chemical provenance indicator 21.42, which is consistent with mafic input as well (Abou
(Potter 1978). The K2O/Na2O ratio (avg. = 2.52, Table 2) re- El-Anwar et al. 2017). In addition, the V–Al2O3 and P2O5–
flects derivation from intermediate or basic rocks. Al2O3 bivariate diagrams can be used to discriminate deposi-
The concentration of the transition trace elements can be tional environments of shales. The V–Al2O3 bivariate plot
used to identify the composition of the source rocks (Garver (Fig. 9) shows that most of studied shale samples plot on
et al. 1996; Armstrong-Altrin 2009). The studied samples shallow marine depositional environments.
have higher contents of some transition metals such as V, The Ni/Co ratio values can be used as an indicator for
Zn, and Cr (average of 376, 255, and 158 ppm, respectively) paleo-redox conditions. The values of Ni/Co ratios below 5
and slightly depleted in some others such as Cu, Ni, and Co indicate oxic environments, whereas values of this ratio above
(average of 48, 47, and 9 ppm, respectively) compared with 5 suggest suboxic and anoxic depositional environments
PAAS. Figure 7 indicates that the source area was dominated (Jones and Manning 1994). Ni/Co ratio of the studied black
by rocks of intermediate type with subordinate of mafic com- shales varies from 5.0 to 12.25 (avg. = 7.1, Table 3) suggest
position. The positive correlation between Cr and Ni (r = 0.98, that the deposition of these shales is performed under suboxic
Table 4) and the Cr/Ni ratios (3.86) revealed that few mafic and anoxic conditions. The values of V/Cr ratios are also
components from the basement source rocks accumulated dur- considered as an indicator of paleo-redox conditions. The
ing weathering. They are probably derived from the basement V/Cr ratio values ranges from 1.28 to 6.5 (avg. = 2.7,
terrains in the Red Sea Hills and transported via Wadi Table 3) which revealed that it was deposited under anoxic
el-Shaghab and Wadi el-Miyah (Fig. 1). conditions (Hallberg 1976). The average value of Mo/Al2O3
The trace element ratios such as La/Sc, La/Co, Th/Sc, ratios of the investigated samples is 0.5, which is slightly
Th/Co, and Cr/Th values of the Upper Cretaceous Duwi higher than the PAAS shale standard value (0.1; Taylor and
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Arab J Geosci (2018) 11:147 Page 15 of 17 147

McLennan 1985), suggest anoxic conditions for studied Armstrong-Altrin JS, Machain-Castillo ML (2016) Mineralogy, geo-
chemistry, and radiocarbon ages of deep sea sediments from the
shales. Such conditions can only result from anaerobic bacte-
Gulf of Mexico, Mexico. J S Am Earth Sci 71:182–200
rial activity. Armstrong-Altrin JS, Lee YI, Verma SP, Ramasamy S (2004)
Geochemistry of sandstones from the Upper Miocene
Kudankulam Formation, southern India: implications for prove-
nance, weathering, and tectonic setting. J Sediment Res 74:285–297
Conclusions Armstrong-Altrin JS, Nagarajan R, Madhavaraju J, Rosales-Hoz L, Lee
YI, Balaram V, Cruz-Martinez A, Avila-Ramirez G (2013)
The Duwi black shales are classified mainly as Fe-shale. Geochemistry of the Jurassic and upper Cretaceous shales from
Compared to PAAS, the shales are highly enriched in SiO2, the Molango Region, Hidalgo, eastern Mexico: implications for
source-area weathering, provenance, and tectonic setting. Compt
Al2O3, CaO, Fe2O3, and P2O5 and highly depleted in TiO2 and
Rendus Geosci 345(4):185–202
Na2O content. The positive correlation between Al2O3 and Armstrong-Altrin JS, Machain-Castillo ML, Rosales-Hoz L, Carranza-
SiO2, TiO2, and Zr indicate a considerable amount of detrital Edwards A, Sanchez-Cabeza JA, Ruíz-Fernández AC (2015a)
clays. K2O shows a positive correlation with both SiO2 and Provenance and depositional history of continental slope sediments
Al2O3, which indicates the association of K2O with alumino- in the Southwestern Gulf of Mexico unraveled by geochemical anal-
ysis. Cont Shelf Res 95:15–26
silicate phases. Armstrong-Altrin JS, Nagarajan R, Balaram V, Natalhy-Pineda O
The CIA, CIW, and PIA values of the Duwi black shales (2015b) Petrography and geochemistry of sands from the
suggest recycle deposits and intensive weathering in the Chachalacas and Veracruz beach areas, western Gulf of Mexico,
source region and reflect warm/humid climatic conditions in Mexico: constraints on provenance and tectonic setting. J S Am
Earth Sci 64:199–216
the depositional basin. The SiO2/Al2O3, Al2O3/Na2O, and Basu A, Bickford ME, Deasy R (2016) Inferring tectonic provenance of
K2O/Na2O ratio values of the Duwi black shales in all studied siliciclastic rocks from their chemical compositions: a dissent.
sites suggest moderate compositional maturity. The ICV Sediment Geol 336:26–35
values of the Duwi black shales (avg. = 1.13) are slightly more Berner RA (1982) Burial of organic carbon and pyrite sulfur in the mod-
ern ocean: its geochemical and environmental significance. Am J
than 1, indicating the presence of detrital ferromagnesian min- Sci 282:451–473
erals beside the abundant clay minerals. Bhatia MR (1985) Rare earth element geochemistry of Australian
The geochemistry results indicate that the Duwi black Paleozoic graywackes and mudrocks: provenance and tectonic con-
shales were mainly derived from the Precambrian gabbro trol. Sediment Geol 45:97–113
Borghesi F, Migani F, Dinelli E (2016) Geochemical characterization of
and metagabbro–diorite complex with subordinate recycled surface sediments from the northern Adriatic wetlands around the Po
sedimentary rocks (Nubia Formation). The Fe2O3/TiO2, Ni/ River delta. Part II: aqua regia results. J Geochem Explor 169:13–29
Co, V/Cr, and Mo/Al2O3 ratio values and the high concentra- Bottcher ME, Hetzel A, Brumsack HI, Schipper A (2006) Sulfur-iron-
tion of Sr, V, Ni, Cr, Zn, and Cd in the investigated Duwi black carbon geochemistry in sediments of the Demerara Rise. Proc ODP
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facilitating analytical work for the present research. Thanks also to the geochemical evidence from the Archean to Early Proterozoic gran-
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