You are on page 1of 17

Arabian Journal of Earth Sciences

Volume 2, No.3, April 2015 ISSN 2409-4730 Pages 23-39

Geochemistry of the Shahat Marl Member, Wadi Az Zad, Al Jabal Al


Akhdar, NE Libya

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).

Al Jabal Al Akhdar is located in Cyrenaica in the northeastern part of Libya.


Al Jabal Al Akhdar essentially consists of Upper Cretaceous to Tertiary marine
deposits, but Jurassic and Lower Cretaceous marine deposits are known from the
exploratory oil wells. The mountain extends to an approximate 400 km in the
northeastern trend. Rohlich (1974) and Klen (1974) divided the Oligocene section in
the Al Jabal Akhdar into a lower Al Bayda Formation and an upper Al Abraq
Formation separated by an unconformity. Rohlich (1974) divided the Al Bayda
Formation into two members: the Shahat Marl and Algal Limestone. The Shahat Marl
Member is developed only on the northern slope of the Al Jabal Al Akhdar but
disappears to the south.

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. 1: Location map of the study area

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.

Materials and methods


The present paper attempts to contribute to the available knowledge on the
geochemical characteristics of the Shahat Marl Member. The work is done according
to the following plan:
1. Nine samples are collected from the studied member (three samples of each unit).
The collected samples were washed thoroughly in distilled water to remove the
contamination.
2. Drying of samples.
3. Grinding of samples.
4. Compression of samples.
5. Bulk geochemical analysis for major oxides and trace elements were performed
using the inductively coupled plasma-mass spectrometry (ICP-MS) technique, which
is widely used, at present, for determination of elements in various materials with
27 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

high precision. The analytical procedure depends on the decomposition of exact


weight of 0.2 g powdered fine sand size sample in 50 ml Teflon beaker.
Decomposition was done by 4 ml HNO3, 3 ml HClO4 and 5 ml HF, and evaporated to
dryness under 200C. The residue was dissolved with 5 ml (1:1) HNO3 by heating and
5 ml of 4 ppm indium solution was added as an internal standard. The sample, as well
as reference, solutions were introduced by peristaltic pump with 0.18 rpm. Before
each measurement, nebulizer and spray chamber were washed by introducing the
solution for 3 min with 0.5 rpm and 30 seconds with 0.18 rpm. The analysis was done
in the ACME analytical laboratories of Vancouver, Canada.

Results and discussions


Major oxides
The concentrations of major oxides and trace elements in the studied
sediments are given in Table 1. The studied samples show small variations in most
major oxide contents. The contents of volatiles (LOI) are remarkably high (avg. 42.50
wt%) due to abundant carbonate and organic material.

The graphical presentation of the correlation coefficients among the analyzed


major oxides points to the intimate coherence among then, except for lime (Fig. 4).
Silica, alumina, iron oxide, magnesia and potash are most probably accommodated
within terrestrial admixture.

Aluminum concentration is a reasonably good measure of detrital flux, the


positive correlations of K2O and MgO with Al2O3 (r = 0.93 and 0.86, respectively)
suggest that they are bound to aluminosilicate minerals and associated phases and,
therefore, they have been concentrated during weathering processes (Zhang, 2004).

The K2O/Al2O3 ratio is important in sedimentary rocks in understanding the


source of aluminum and its distribution between clay and feldspars minerals (Katongo
et al., 2004). The K2O/Al2O3 ratios for clay minerals and feldspars are different (0.0
to 0.3, 0.3 to 0.9, respectively; Cox et al., 1995). In the studied samples, the
28 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

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

Iron oxide Magnesia

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.

PAAS-normalized REE patterns of the studied samples are shown in Fig. 6.


The studied member shows more or less flat REE pattern with positive La and slight
negative Ce anomalies (Table 2). The studied samples show slight negative and
positive Eu anomalies.

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

Fig. 6: PAAS normalized REE diagram of the Shahat Marl Member

Table 2: REE parameters in the Shahat Marl Member


(Concentrations are given in ppm)
Unit Unit 1 Unit 2 Unit 3
Sample No. 1a 1b 1c 2a 2b 2c 3a 3b 3c
LREE 5.65 6.66 7.49 17.64 12.36 14.20 37.38 27.56 23.75
HREE 1.04 1.14 1.00 3.09 2.04 1.49 5.40 3.12 2.71
REE 6.69 7.80 8.49 20.73 14.40 15.69 42.78 30.68 26.46
Er/Nd 0.16 0.16 0.12 0.14 0.13 0.06 0.11 0.08 0.09
Y/Ho 48.83 38.14 32.83 33.65 36.00 27.25 35.63 31.18 27.94
La 1.14 1.30 0.95 1.00 1.11 0.43 1.10 1.02 1.03
Ce 0.89 0.91 0.94 0.94 0.90 0.96 0.89 0.80 0.99
Eu 1.24 1.11 0.92 0.92 1.02 0.93 1.03 1.02 0.93
31 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

The average REE concentrations of limestone are more or less comparable


with typical marine carbonate value (~28 ppm) (Bellanca, 1997). The PAAS
normalized REE patterns of limestone were expected the retention of seawater
characteristics including: (1) uniform light REE depletion, (2) a negative Ce anomaly,
and (3) a slight positive La anomaly (Bau and Dulski, 1999). Additionally, seawater
Y/Ho ratios are distinctively high, for their different complexation behavior in
surface. However, a few of the REE patterns obtained in this study do not conform to
typical seawater patterns. Thus the possibility of sources from contamination needs to
be assessed carefully before deducing chemical peculiarities for the precipitating
waters and thus depositional environments. The major possible sources of
contamination include: (1) terrestrial particulate matter, which is a major source for
marine REE, without the seawater-like patterns (e.g. shale); (2) Fe and Mn oxides; (3)
phosphates, which have a high affinity for REE in diagenetic fluid (Northdurft, 2004).

Previous research showed that as little as 2% shale contaminations could


change REE patterns (Northdurft, 2004; Song et al., 2014). Trace elements (such as
Zr and Th) could infer terrigenous material, what are concentrated in different detrital
minerals. Good positive correlations between REE with Zr and Th (r = 077 and 0.81,
respectively) of samples were expected for terrestrial clastic contaminating.

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.

Eu is the only REE showing a changing valency in the near surface


environment, where Eu3+ was reduced to Eu2+ under extremely reducing conditions.
Redox potential of Eu in aqueous solutions depends mainly on temperature and to a
lesser extent on pressure, PH, and REE speciation (Bau and Dulski, 1996), which
explains that the positive Eu anomalies are typically found in acidic, reducing
hydrothermal fluids.

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.

The Ce anomalies in marine carbonate rocks have been considered as suitable


indicator for understanding contemporaneous paleo-redox conditions (Liu et al.,
1988). Many studies have been undertaken on Ce behavior in marine phases to
unravel paleoceanographic conditions (e.g., Liu et al., 1988; Nath et al., 1997;
Madhavaraju and Gonzalez-Leon, 2012). As marine water shows negative Ce,
33 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

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).

Y is inserted between Ho and Dy in the REE pattern according to its identical


charge and similar radius (Bau and Dulski 1996). The terrigenous materials and
volcanic ash have constant chondritic Y/Ho ratio of ~28, and seawater generally
displays high Y/Ho ratios (from 44 to 74) (Song et al., 2014). Y/Ho ratios express a
significant variation among the open-ocean seawater and the ocean margin seawater
(Nozaki et al., 1997). Although Y and Ho have similar ionic radius, identical charge
and thus similar geochemical behavior, Ho is removed from seawater twice as fast as
Y, because of the differences in the surface complexation behavior (Nozaki et al.,
1997). Thus, the Y/Ho ratios are different between marine and non-marine deposits
(Bau and Dulski 1996; Northdurft, 2004).

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

References
Bau, M. and Dulski, P. (1996): Anthropogenic origin of positive gadolinium
anomalies in river waters. Earth and Planetary Science Letters; 143: 245-255.

Bau, M. and Dulski, P. (1999): Comparing yttrium and rare earths in hydrothermal
fluids from the Mid-Atlantic Ridge: Implications for Y and REE behavior during
near-vent mixing and for the Y/Ho ratio of Proterozoic seawater. Chemical Geology;
155: 77-90.

Bellanca, A.; Masetti, D. and Neri, R. (1997): Rare-earth elements in limestone/


marlstone couplets from the Albian-Cenomanian Cismon section (Venetian region,
northern Italy): Assessing REE sensitivity to environmental changes. Chemical
Geology; 141: 141-152.

Bolhar, R. and Van Kranendonk, M.J. (2007): A non-marine depositional setting for
the northern Fortescue Group, Pilbara Craton, inferred from trace element
geochemistry of stromatolitic carbonates. Precambrian Research; 155: 229-250.

Cox, R.; Low, D.R. and Cullers, R.L. (1995): The influence of sediment recycling and
basement composition on evolution of mudrock chemistry in the southwestern United
States. Geochimica et Cosmochimica Acta; 59: 2919-2940.

De Baar, H.J.W.; German, C.R. and Elderfield, H. (1988): Rare-earth element


distributions in anoxic waters of the Cariaco Trench. Geochimica et Cosmochimica
Acta; 52: 1203-1219.

De Baar, H.J.W.; Schijf, J. and Byrne, R.H. (1991): Solution chemistry of the rare
earth elements in seawater. European Journal of Solid State Inorganic Chemistry; 28:
357-373.
36 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

Elderfield, H. (1988): The oceanic chemistry of the rare earth elements. Philosophical
Transactions of the Royal Society of London; 325: 105-106.

Frimmel, H.E. (2009): Trace-element distribution in Neoproterozoic carbonates as


palaeoenvironmental indicator. Chemical Geology; 258: 338-353.

German, C.R.; Holliday, B.P. and Elderfield, H. (1993): A geochemical study of


metalliferous sediment from the TAG hydrothermal mound, 2608 N, Mid-Atlantic
ridge. Journal of Geophysical Research; 98: 9683-9692.

Katongo, C.; Koeberl, C.; Witzke, B.J.; Hammond, R.H. and Anderson, R.R. (2004):
Geochemistry and shock petrography of the Crow Creek Member, South Dakota,
USA: Ejecta from the 74-Ma Manson impact structure. Meteoritics and Planetary
Science; 39(1): 31-51.

Klen, L. (1974): Geological map of Libya, 1:250000 sheet Benghazi NI 34-14,


Explanatory Booklet, Indust. Res. Cent.,Tripoli, p 56.

Kurian, S.; Nath, B.N.; Ramaswamy, V.; Naman, D.; Gnaneshwar Rao; Kamesh Raju,
K.A.; Selvaraj, K. and Chen, C.T.A. (2008): Possible, detrital, diagenetic and
hydrothermal sources for Holocene sediments of the Andaman backarc basin. Marine
Geology; 247: 178-193.

Liu, S.; Liu, Y.; Lin, G.; Zhou, Y.; Gong, F. and Zhang, D. (2006): REE geochemical
characteristics and geological significance of mudstones from Neogene, Nanpu Sag,
Bohai Basin. Geoscience; 20: 449-456.

Liu, Y.G.; Miah, M.R.U. and Schmitt, R.A. (1988): Cerium: a chemical tracer for
paleo-oceanic redox conditions. Geochimica et Cosmochimica Acta; 52: 1361-1371.
37 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

MacLeod, K.G. and Irving, A.J. (1996): Correlation of cerium anomalies with
indicators of paleoenvironment. Journal of Sedimentary Research; 66: 948-955.

MacRae, N.D.; Nesbitt, H.W. and Kronberg, B.I. (1992): Development of a positive
Eu anomaly during diagenesis. Earth and Planetary Science Letters; 109: 585-591.

Madhavaraju, J.; Gonzalez-Leon, C.M.; Lee, Y.I.; Armstrong-Altrin, J.S. and Reyes-
Campero, L.M. (2010): Geochemistry of the Mural Formation (Aptian-Albian) of the
Bisbee Group, Northern Sonora, Mexico. Cretaceous Research: 31: 400-414.

Madhavaraju, J. and Gonzalez-Leon, C.M. (2012): Depositional conditions and source


of rare earth elements in carbonate strata of the Aptian-Albian Mural Formation,
Pitaycachi section, northeastern Sonora, Mexico. Revista Mexicana de Ciencias
Geologicas; 29(2): 478-491.

Madhavaraju, J. and Lee, Y.I. (2009): Geochemistry of the Dalmiapuram Formation


of the Uttatur Group (Early Cretaceous), Cauvery basin, southeastern India:
Implications on provenance and paleo-redox conditions. Revista Mexicana de
Ciencias Geolgicas; 26(2): 380-394.

Michard, A.; Albarede, F.; Michard, G.; Minister, J.F. and Charlow, J.L. (1983): Rare
earth elements and uranium in high temperature solutions from East-Pacific rise
hydrothermal vent field (13N): Nature; 303: 795-797.

Nath, B.N.; Bau, M.; Ramlingeswara-Rao, B. and Rao, C.M., (1997): Trace and rare
earth elemental variation in Arabian Sea sediments through a transect across the
oxygen minimum zone. Geochimica et Cosmochimica Acta; 61: 2375-2388.

Northdurft, L.D.; Webb, G.E. and Kamber, B.S. (2004): Rare-earth element
geochemistry of Late Devonian reefal carbonates, Canning Basin, Western Australia:
38 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

Confirmation of seawater REE proxy in ancient limestones. Geochimica et


Cosmochimica Acta; 68: 263-283.

Nozaki, Y.; Zhang, J. and Amakawa, H. (1997): The fractionation between Y and Ho
in the marine environment. Earth and Planetary Science Letters; 148: 329-340.

Rohlich, P. (1974): Geological Map of Libya; 1:250,000 sheet: Al Bayda NI 34-15.


Explanatory Booklet, Ind. Res. Centre, Tripoli. 70 pp.

Shaltami, O.R. (2012): Mineral composition and environmental geochemistry of the


beach sediments along the Mediterranean Coast from Benghazi to Bin Jawwad,
Northeast Libya. PH.D. Thesis. Cairo Univ. Cairo, Egypt.

Sholkovitz, E.R.; Landing, W.M. and Lewis, B.L. (1994): Ocean particle chemistry:
the fractionation of rare earth elements between suspended particles and seawater.
Geochimica et Cosmochimica Acta; 58: 1567-1579.

Song, C.; Herong, G. and Linhua, S. (2014): Geochemical characteristics of REE in


the Late Neoproterozoic limestone from northern Anhui Province, China. Chin.J.
Geochem; 33:187-193.

Taylor, S.R. and McLennan, S.M. (1985): The Continental Crust: its composition and
evolution. Blackwell Scientific Publishers, Oxford.

Verma, S.P. (2005): Estadstica Bsica para el Manejo de Datos Experimentales:


Aplicacin en la Geoqumica (Geoguimiometra): Mxico, D.F., Universidad
Nacional Autnoma de Mxico, 186pp.

Zhao, Y.; Zheng, Y. and Chen, F. (2009): Trace element and strontium isotope
constraints on sedimentary environment of Ediacaran carbonates in southern Anhui,
South China. Chemical Geology; 265: 345-362.
39 Arabian Journal of Earth Sciences Volume 2, No.3, April 2015

Zhang, K.J. (2004): Secular geochemical variations of the Lower Cretaceous


siliciclastic rocks from central Tibet (China) indicate a tectonic transition from
continental collision to back-arc rifting. Earth and Planetary Science Letters; 229: 73-
89.

You might also like