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O.R. Shaltami
Department of Earth Science, Faculty of Science, Benghazi University, Libya
Abstract
The present paper describes the geochemical characteristics of the Shahat Marl
Member, at Wadi Az Zad, Al Jabal Al Akhdar, NE Libya. The exposed section of the
Shahat Marl Member consists of marly limestones. Bulk geochemical analysis for
major oxides and trace elements were performed using the ICP-MS technique. The
graphical presentation of the correlation coefficients among the analyzed major oxides
points to the intimate coherence among then, except for lime. Silica, alumina, iron
oxide, magnesia and potash are most probably accommodated within terrestrial
admixture. The PAAS-normalized REE patterns are characterized by (1) more or less
flat REE pattern (2) slight negative Ce and positive La anomalies and (3) Slight
negative and positive Eu anomalies. The character indicated that the depositional
environment was oxygenated, with infection by the hydrothermal activity and
contamination of detritus.
Keywords: Geochemical Characteristics, Major Oxides, Rare Earth Elements, Shahat Marl
Member, Wadi Az Zad, Al Jabal Al Akhdar, Libya
Introduction
Rare-earth elements (REE) concentrations were highly interested by many
geologists for their unique characteristics. A series of previous studies have shown
that chemically sedimentary rocks (e.g. carbonate or banded iron formation) are
useful proxies for the recording of REE patterns in the water where they were
precipitated (e.g., Northdurft, 2004; Bolhar and Van Kranendonk, 2007; Frimmel,
2009; Madhavaraju and Gonzalez-Leon, 2012; Song et al., 2014). Though the REE
24 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
concentrations in carbonate rocks are low, they are useful to identify the marine
versus non-marine sources of REE (Zhao et al., 2009). REE is considered as an
indicator to identify the depositional environmental system (such as widespread
marine anoxia, oceanic redox conditions, proximity to source area, lithology and
diagenesis, and paleogeography and depositional models), for the distribution of REE
is sensitive to water depth, salinity, oxygen level, and input sources (Northdurft,
2004).
The previous study showed that marine chemical sediments (e.g. carbonates)
are characterized by a uniform light REE depletion, a negative Ce anomaly, a slight
positive La anomaly and remarked positive Y anomaly in PASS-normalized
diagrams, which are conform to the seawater REE patterns (Northdurft, 2004),
however, the acidic hydrothermal fluids show very different REE patterns (e.g.
positive Eu anomaly and MREE enriched) (Bau and Dulski, 1999).
The present paper describes the geochemical characteristics of the Shahat Marl
Member, at Wadi Az Zad, Al Jabal Al Akhdar, NE Libya. The Wadi Az Zad is
located in the lower escarpment of Al Jabal Al Akhdar about 70 Km northeast of
Benghazi city, NE Libya (Fig. 1). The exposed section of the Shahat Marl Member is
about 50 m thick. The studied section consists of three units (Figs. 2-3).
25 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
Fig. 2: The exposed section of the Shahat Marl Member at Wadi Az Zad
26 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
Fig. 3: Generalized lithostratigraphic column of the Shahat Marl Member in the study
area
As far as the author is aware, the published data on the Shahat Marl Member is
scanty. Most geological publications on the studied member deal with the sedimentary
succession with especial attention to fossil content.
K2O/Al2O3 ratio is about 0.27, indicating that clay minerals have a major role in the
distribution of aluminum in the Shahat Marl Member.
Table 1: Chemical analysis data (major oxides in wt%, trace elements in ppm) of the
Shahat Marl Member
Member Shahat Marl
Unit 1 2 3
Sample No. 1a 1b 1c 2a 2b 2c 3a 3b 3c
SiO2 0.90 0.83 1.04 2.93 3.06 3.00 1.12 1.19 1.15
Al2O3 0.31 0.27 0.40 0.58 0.70 0.66 0.33 0.41 0.38
Fe2O3 0.14 0.09 0.09 0.35 0.28 0.31 0.18 0.16 0.16
MnO 0.01 0.02 0.02 0.01 0.01 0.01 0.01 0.03 0.03
MgO 1.10 1.26 1.00 1.53 1.69 1.55 1.24 1.20 1.17
CaO 51.85 51.91 52.00 53.27 53.08 52.97 54.03 53.76 53.67
K2O 0.08 0.07 0.10 0.13 0.20 0.17 0.10 0.14 0.11
Cl 0.16 0.13 0.13 0.03 0.06 0.04 0.31 0.33 0.29
SO3 0.12 0.16 0.15 0.12 0.11 0.11 0.20 0.16 0.17
LOI 44.40 44.77 45.06 40.37 40.28 41.00 41.91 42.09 42.61
Total 99.07 99.51 99.99 99.32 99.47 99.82 99.43 99.47 99.74
Pb 1.87 1.73 1.15 1.20 1.44 0.98 2.81 2.11 0.96
Zr 3.16 5.03 6.51 18.50 8.32 10.20 15.50 20.50 23.13
Th 0.77 0.49 0.46 1.48 0.99 0.24 1.69 1.32 1.31
Y 2.93 2.67 1.97 5.72 4.68 2.18 11.40 5.30 4.47
La 1.36 1.70 1.81 3.98 2.97 1.81 9.15 7.29 5.61
Ce 2.46 2.96 3.45 7.93 5.47 7.51 16.50 11.70 11.21
Pr 0.30 0.33 0.40 0.96 0.66 0.89 1.98 1.54 1.22
Nd 1.20 1.32 1.46 3.77 2.61 3.26 7.71 5.71 4.61
Sm 0.26 0.28 0.31 0.83 0.53 0.62 1.68 1.09 0.92
Eu 0.07 0.07 0.06 0.17 0.12 0.11 0.36 0.23 0.18
Gd 0.27 0.31 0.30 0.90 0.57 0.50 1.61 1.03 0.89
Tb 0.05 0.05 0.05 0.14 0.09 0.08 0.25 0.16 0.13
Dy 0.28 0.28 0.25 0.79 0.53 0.37 1.39 0.81 0.67
Ho 0.06 0.07 0.06 0.17 0.13 0.08 0.32 0.17 0.16
Er 0.19 0.21 0.17 0.52 0.34 0.21 0.85 0.46 0.41
Tm 0.02 0.03 0.02 0.07 0.04 0.03 0.12 0.06 0.06
Yb 0.15 0.17 0.13 0.43 0.30 0.19 0.75 0.38 0.34
Lu 0.02 0.02 0.02 0.07 0.04 0.03 0.11 0.05 0.05
29 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
Silica
Potash
Alumina
Lime
Fig. 4: Correlations among the major oxides in the Shahat Marl Member (intensity of
lines corresponds to the strength of the correlation coefficient (< 0.4 to > 0.8)
Trace elements
Trace element concentrations of the Shahat Marl Member were normalized against
Post-Archean Australian Shale (PAAS) values (Taylor and McLennan, 1985) and are
plotted in Fig. 5. The trace elements in the present study are clearly depleted with
respect to those of PAAS.
1.00
Samples/PAAS
0.10
0.01
Pb Zr Th Y REE
Fig. 5: Trace elements content of Shahat Marl Member normalized to the PAAS
(Taylor and McLennan, 1985)
In the present study, Th, Y and REE are positively correlated with CaO (r =
0.78, 0.74 and 0.93, respectively). In agreement with Verma (2005) and Shaltami
30 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
(2012), these relations suggest that Th, Y and REE may be bound in calcite. The
variations in REE concentrations in the different litho-units of the Shahat Marl
Member are probably controlled by the amount of calcite.
14
Unit 1
Unit 2 O
Unit 3
Samples/PAAS
0
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
The value of Er/Nd ratio is about 0.27 in normal seawater (De Baar et al.,
1988). The high Er/Nd ratio of limestone effectively reveals the seawater signature
retained by the marine carbonate. The detrital material or diagenesis can reduce the
Er/Nd value to lower than 0.1, for the preferential concentration of Nd relative to Er
(Bellanca, 1997). In the studied samples, the Er/Nd ratios are ranging from 0.120.16
in unit 1, 0.060.14 in unit 2 and 0.080.11 in unit 3 (see Table 2), with a good
positive correlation between Nd and Er (r = 0.91), indicating that the influence of
detrital materials in the studied limestones are reliable.
Diagenesis would change the values of Ce and Eu anomalies along with good
correlations between Ce and REE, and between Ce and Eu (Liu et al., 2006). In
32 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
the present study, Eu and REE show weak negative correlations with Ce (r = -0.42
and -0.19, respectively), suggesting that the affection of diagenesis process on the
REE concentrations is limited.
The studied sediments show slight negative and positive Eu anomalies (see
Table 2). Positive Eu anomalies are uncommon in seawater, which is generally
resulted by these actors: (1) an increased oceanic input of hydrothermally originated
fluids at mid oceanic ridges (Michard et al., 1983; German et al., 1993; Kurian et al.,
2008); (2) a slight increase in the primary or detrital feldspar component (Nath et al.,
1992; Madhavaraju et al., 2010); (3) the diagenetic alteration in the limestone
(MacRae et al., 1992) or (4) as result of eolian input (Elderfield, 1988). Elements like
Zr and Th are useful for understanding the presence of detrital feldspar in the bulk
sediments. In the present study, Eu is negatively correlated with Zr (r = -0.61),
which suggests that the positive Eu anomaly in the limestone may not be due to the
detrital inclusion. Weak negative correlations between Ce and REE (r = -0.19), and
between Ce and Eu (r = -0.42) also suggest that the affection of diagenetic process
on REE concentrations is limited. In agreement with Song et al., (2014) the writer
believes that the positive Eu anomalies are produced by the hydrothermal activity.
similar Ce anomaly in limestones reveals the inclusion of REE directly from seawater
or pore water under oxic condition. The deficiency of Ce relative to neighboring rare
earth elements is an important feature of modern seawater. This can be explained by
oxidation of trivalent Ce to less soluble tetravalent Ce and successive removal by
suspended particles through scavenging process (Sholkovitz et al., 1994). However,
Ce is remobilized and released into the water column in the suboxic environment
resulting in a less negative to positive anomaly in seawater (De Baar et al., 1991).
But, the precise measurements of Ce anomalies in marine sediments may constrain
redox conditions at the time and place of deposition (MacLeod and Irving, 1996).
In the studied member, the slight negative Ce anomalies could suggest that
these limestones were deposited in oxygenated environment. In addition, Ce values
are negatively correlated with scavenging-type particle reactive elements (Ce vs. Pb:
r = -0.60), in agreement with shallow marine depositional environments
(Madhavaraju and Lee, 2009).
In the studied samples, the Y/Ho ratios are ranging from 27.25 to 48.83 (see
Table 2), indicating that the studied sediments preserve the seawater information,
though contaminated by the influence of terrigenous materials.
34 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
Conclusions
The present paper describes the geochemical characteristics of the Shahat Marl
Member, at Wadi Az Zad, Al Jabal Al Akhdar, NE Libya. The exposed section of the
Shahat Marl Member consists of marly limestones. Bulk geochemical analysis for
major oxides and trace elements were performed using the ICP-MS technique. The
graphical presentation of the correlation coefficients among the analyzed major oxides
points to the intimate coherence among then, except for lime. Silica, alumina, iron
oxide, magnesia and potash are most probably accommodated within terrestrial
admixture. Th, Y and REE are positively correlated with CaO. These relations suggest
that Th, Y and REE may be bound in calcite. The studied member shows more or less
flat REE pattern with positive La and slight negative Ce anomalies. The studied
samples show slight negative and positive Eu anomalies. Good positive correlations
between REE with Zr and Th were expected for terrestrial clastic contaminating. Eu
and REE show weak negative correlations with Ce, suggesting that the affection of
diagenesis process on the REE concentrations is limited. Eu is negatively correlated
with Zr, which suggests that the positive Eu anomaly in the limestone may not be due
to the detrital inclusion. The writer believes that the positive Eu anomalies are
produced by the hydrothermal activity. The slight negative Ce anomalies could
suggest that these limestones were deposited in oxygenated environment. In addition,
Ce values are negatively correlated with Pb, in agreement with shallow marine
depositional environments. The Y/Ho ratios are ranging from 27.25 to 48.83,
indicating that the studied sediments preserve the seawater information, though
contaminated by the influence of terrigenous materials.
Acknowledgements
First and forever thanks to God for everything. All gratefulness is due to
almighty Allah the lord of the world who guided and aided me to bring forth this
work. Thanks God. I am grateful to Prof. Ahmed Al-Kammar for the beneficial
comments and improving my manuscript. Thanks are due to ACME analytical
laboratories of Vancouver, Canada for their measurement of major oxide and trace
element concentrations.
35 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015
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