Journal of African Earth Sciences 123 (2016) 350e369

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Journal of African Earth Sciences

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Heavy mineral concentrations in the sandstones of Amij Formation

with particular emphasis on the mineral chemistry and petrographic
characteristics of monazite, western desert of Iraq
Yawooz A. Kettanah a, b, *, Sabah A. Ismail c
a
Department of Geology, College of Science, Salahaddin University, Kirkuk Road, Erbil, Iraq
b
Department of Earth Sciences, Faculty of Graduate Studies, Dalhousie University, Halifax, NS, B3H 4R2, Canada
c
Department of Applied Geology, College of Sciences, Kirkuk University, Kirkuk, Iraq

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

Article history: The heavy minerals in the clastic unit of the Lower Jurassic Amij Formation exposed in the western desert
Received 19 March 2016 of Iraq were studied. The uppermost part of the clastic unit contains thin, placer-like black sandstone
Received in revised form horizons that are radioactive and abnormally rich in heavy minerals (0.6e56%), dominated by opaque
18 June 2016
(65%) and transparent (35%) heavy minerals. The minerals, in the order of decreasing abundance are
Accepted 21 June 2016
Available online 23 June 2016
pseudorutile, goethite, zircon, hematite, magnetite, monazite, rutile, leucoxene, tourmaline, ilmenite,
chromite, and few others. Electron probe microanalysis (EPMA), microscopic and autoradiographic ob-
servations and analysis showed that the monazite is monazite-(Ce) type with an average composition of
Keywords:
Amij formation
(Ce0.39Nd0.16La0.19Pr0.04Sm0.02Gd0.02Eu0.01Y0$04Th0$06U0$01Ca0$05Fe0.01)(P0$98Si0.03)O4.
Iraq Monazite consists predominantly of REE-oxides (57.93%) and P2O5 (29.31%), with minor amounts of
Black sandstones ThO2 (6.60%), Y2O3 (1.92%), UO2 (0.76%), CaO (1.14%), SiO2 (0.69%), and FeOt (0.17%). The dominant
Heavy minerals compositional substitution operating between REE and P were a mixture of the complex cheralite type
Monazite substitution ([REE]
2 [Th][Ca]) and the coupled huttonite type substitution ([REE]
1 [P]
1 [Th][Si]). The
Mineral chemistry chondrite-normalized REE distribution patterns of monazite show enrichment in LREE with positive Eu-
Radioactivity and Pr-anomalies of 1.46 and 9.13, respectively. The median values of (La/Sm)CN and (La/Nd)CN ratios are
LREE
4.35 and 1.97, respectively. Zircon which is the dominant transparent mineral is Hf-rich that is composed
EPMA
of 30.61% SiO2, 57.58% ZrO2, 7.03% HfO2, 2.04% Y2O3, 0.56% ThO2, 0.19% UO2, and 0.19% Al2O3 corre-
sponding to a formula (Zr0.909Hf0.065Th0$004U0$001Y0.031)S1.011(Si3$966Al0.028)S0.999O4. Rutile and tourma-
line form 7% and 4% of the heavy minerals. Ilmenite which is one of the predominant heavy minerals
forms 2.5% of the opaques because it is pervasively altered to Ti-Fe oxides. In addition of zircon and
monazite, the chemical compositions of most of the other heavy minerals are also given in this study. The
expected dominant source of heavy minerals and their host sandstones are most probably the felsic
igneous and metamorphic complexes of the Arabian Shield, currently located ~600 kms to the south of
the studied area. The heavy minerals were carried from the source area by northward moving rivers and
sorted out by ocean waves as black sand concentrations at the delta mouth along the southern beaches of
the Neo-Tethys Ocean under passive margin tectonic setting. This border was apparently bordering the
current western part of Iraq during Upper Jurassic period.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction advancements of single-mineral analytical techniques such as

electron probe microanalysis (EPMA) and Laser Ablation Inductively
Heavy mineral studies have benefited from technology Coupled Mass Spectrometry (LA-ICP-MS) (Mange and Wright,
2007). Interest is generated by those interested in provenance
studies, as well as their economic importance. Monazite in partic-
* Corresponding author. Department of Geology, College of Science, Salahaddin ular has attracted much scientific and economic interest (e.g.,
University, Kirkuk Road, Erbil, Kurdistan Governorate, Iraq. Levinson, 1966; Overstreet, 1967; Graeser and Schwander, 1987;
E-mail addresses: Yawooz.Kettanah@su.edu.krd, kettanah@dal.ca
Nickel and Mandarino, 1987; Masau et al., 2002; Huminicki and
(Y.A. Kettanah), sabah@uow.edu.au (S.A. Ismail).

http://dx.doi.org/10.1016/j.jafrearsci.2016.06.017
1464-343X/© 2016 Elsevier Ltd. All rights reserved.
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 351

Hawthorne, 2002; Mange and Morton, 2007; Linthout, 2007) for it associated heavy minerals and their host sandstones will also be
accommodates significant quantities of lanthanides (REE and Y) and described and discussed in some detail.
phosphorus, and in many occurrences, the actinide thorium (Th).
Monazite-(REE)PO4 is an anhydrous rare-earth elements ortho-
2. Geology
phosphate with monoclinic structure (space group P21/n, Z ¼ 4)
where the larger trivalent rare-earth element (REE) cations are
The rocks of Amij Formation were introduced as a new forma-
located in a polyhedron, coordinated by nine oxygen atoms
tion within the stratigraphic column of western desert of Iraq by
(Huminicki and Hawthorne, 2002; Boatner, 2002). It is basically a
Buday and Hak (1980) (Figs. 1 and 2). They subdivided the forma-
Ce-phosphate with ideal formula of CePO4 where Ce can partially be
tion into two rock units, the lower coastal deltaic or coastal closed
replaced up to few per cent by other light rare earth elements
basin sandstone unit, and the upper carbonate unit of shallow
(LREEs) and Gd, and by some tenths of percent of Eu and heavy rare
coastal marine origin (Fig. 3). The age of the formation is not agreed
earth elements (HREEs) (Nagy and Draganits, 1999). In addition to
upon, ranging between Liasic to Bathonian. Since the introduction
cations of LREEs, monazite may also incorporate significant amounts
of Amij Formation, it was studied by many researchers (e.g., Karim
of thorium, and to a lesser extent, uranium, such that it represents a
and Ctyroky, 1981; Al-Mubarak and Amin, 1983; Jassim et al., 1984;
principal thorium ore, and a secondary source of uranium (Boatner,
Hussein, 1984; Al-Naqib et al., 1986; Qaddouri, 1986; Al-Sinjeri,
2002). Monazite is widely distributed as an accessory mineral in
1987; Al-Hadithi, 1989; Kaseer et al., 1992). The thickness of the
acidic igneous rocks (granites, rhyolites, pegmatites), and gneisses
lower clastic unit of Amij Formation varies between 9 and 21 m and
(Boatner, 2002) and also in carbonatites, charnockites, migmatites,
that of the upper carbonate unit reaches 30 m (Al-Naqib et al.,
and quartz veins (Rapp and Watson, 1986). Monazite of meta-
1986). It is unconformably overlaying the Hussainiyat Formation
morphic origin has been reported, particularly in Ca-poor rocks
(Lower Liassic) and unconformably overlain by the sandstones of
(Nagy and Draganits, 1999; Pan, 1997; Lanzirotti and Hanson, 1996;
Muhaiwir and Saggar formations (Jassim et al., 2006) (Fig. 2).
Akers et al., 1993; Grauch, 1989; Kiesl et al., 1983). It may also be
The Amij Formation was the focus of many studies because of its
found as a heavy mineral in alluvial deposits (placers) such as black
anomalous radioactive nature that was reported by Rohan (1979)
beach sands, where it forms important economic deposits in many
and Polytechnic (1980) (e.g., Al-Kazzaz, 1985; Al-Najim and Hakki,
countries including the United States, Australia, South Africa, Sri
1986; Al-Amiri, 1988; Al-Salihi, 1989; Al-Ameer et al., 1993; Ismail,
Lanka, Brazil, India, Malagasy, and Canada (Boatner, 2002). These
1996; Gayara and Ismail, 1996). Ismail (1996) was the first to fully
detrital deposits were formed by the weathering and erosion of
establish the real causes of radioactivity in Amij Formation and
granitic and other related host rocks. The formation of such
concluded that the main source of such anomalous radioactivity is
monazite placer deposits is attributed to its mechanical and
mainly monazite and to a lesser degree zircon; meanwhile the
chemical stability such that it survives metamorphic and sedi-
previous studies attributed the radioactivity mostly to zircon. The
mentary cycles for 100s million years (Rapp and Watson, 1986). In
currently studied heavy mineral-rich horizons occur as few centi-
addition to the economic importance of monazite as the source of
metres thick each, blanket-like, highly concentrated black sand-
REE, Th and U, it also has many scientific applications. Monazite has
stone beds alternating with white sandstones which were
been used in provenance studies as tectonic indicator (Drost et al.,
deposited as beach sands along the southern coast of the Tethys Sea
2004); geochronology for Th-U-Pb age dating (Krenn et al., 2009;
during Jurassic Period. The economic significance of this occurrence
Kusiak et al., 2006; Gonzalez-Alvarez et al., 2006; Yang et al.,
is not fully studied although its radioactivity has been detected by
2006; Williams et al., 2007), and in geothermometry and geo-
carborne survey.
barometry (Gratz and Heinrich, 1997, 1998; Andrehs and Heinrich,
The western desert is part of the Stable Shelf tectonic division of
1998).
Iraq which includes formations ranging in age from Permo-
The heavy minerals and their host clastic lower part of the Amij
Carboniferous to Tertiary. These formations were deposited in
Formation including a proposed heavy-mineral placer deposit, very
continental to shallow marine environments, and are separated by
rich in opaques and transparent minerals (zircon, monazite, rutile,
regional to local unconformities (Fig. 2). In spite of the relative
and tourmaline and others) form the uppermost part of the sand-
stability of the area, it has been affected by tectonism that may be
stone unit exposed in the western desert of Iraq are studied. The
observed in the sedimentation modes and is reflected in regional
study gives particular emphasis to monazite which is the main
structural features that controlled structural development of the
source of radioactivity of the Amij Formation. The Lower Jurassic
sedimentary basin. The most important structural feature is the
Amij Formation is best exposed in Amij valley area (locally called
Rutba Uplift which is the extension of the Hail-Rutba Arch. The
Wadi Amij), some 50 km east of Rutba City (Fig. 1). Anomalous
effect of this structure is evident from the lack of sedimentation and
radioactivity in Amij Formation was reported by Rohan (1979) and
presence of unconformities during Mesozoic and Cenozoic periods
Polytechnic (1980) which were followed by subsequent studies
(Buday and Hak 1980). These events have affected the mode of
investigating the source of radioactivity and its possible economic
sedimentation during Jurassic period in the form of sedimentation
importance. However, the main source of the radioactivity were not
cycles characterized by clastic strata forming the lower part,
fully identified until the work of Ismail (1996) who described
separated by unconformities from older units, and covered by
monazite to be the main cause of the radioactive anomaly, with a
carbonate strata surrounding the Rutba Uplift which are exposed in
minor contribution from zircon. Before the study of Ismail (1996),
the east of Rutba City. The western desert has very low relief, ~2 m/
zircon was considered as the main radioactivity source by most of
km with a NE-SW regional strike of the Jurassic formations (Fig. 2).
previous studies. The importance of Amij Formation is also high-
lighted by Al-Bassam (2007) as an important formation for its
heavy minerals content. 3. Sampling and methodology
The description includes the mineralogical, geochemical, opti-
cal, autoradiographic and separation characteristics of monazite as 225 samples were collected from the Amij Formation along 20
well as its provenance, which forms ~8% of heavy minerals within sections that were exposed in 17 trenches dug within the Amij
the studied sandstones. In addition to monazite, data about the Valley and 3 trenches to the northeast of the valley (Fig. 1). The
samples comprised 185 sandstones and 40 claystones.
352 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

Fig. 1. Geologic map of the study area (top left) showing the location of the three sampled trenches (K, L, M) and enlarged map view of part of Amij Formation showing the
configuration of Amij Valley (Wadi) and the locations of the seventeen sampled sections.

Fig. 2. Geologic map of the western desert of Iraq, scale 1:2000,000 (from Sissakian and Mohammed (2007); the legend is rearranged by the current authors).

The thin sections of sandstones and 55 heavy minerals polished polarizing microscopes. The heavy minerals were concentrated
thin sections were studied under transmitted and reflected light using bromoform heavy liquid under standard separation
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369
Fig. 3. Typical cross-section through the Amij Formation; the thickness of the upper
carbonate unit is up to 30 m and that of the lower clastic unit is 9e21 m.
procedures. Individual transparent heavy minerals were separated
from the heavy mineral concentrates using Franz isodynamic
magnetic separator and further purified by hand picking under
binocular microscope.
Electron Microprobe analysis of the heavy minerals were con-
ducted at Nagoya University Center for Chronological Research
(Japan), Dalhousie University (Canada), and Uppsala University
(Sweden). Monazite grains were analysed in Japan and Canada,
zircon in Japan; meanwhile ilmenite, rutile and the other Fe-Ti
oxides were analysed in Sweden. Zircon and monazite were ana-
lysed in Japan using JEOL JXA-733 electron microprobe provided
with 3 WDS spectrometers that have a 140 mm radius Rawland
circle, each equipped with TAP, PET and LiF diffraction crystals and a
sealed Xe X-ray detector. The instrument was operated at 15 kV
accelerating voltage, 0.02e0.15 mA probe current and 5 mm probe
diameter. X-ray intensities were integrated over 40 s at peak po-
sitions and over 20 s at two background positions. The details of the
analytical conditions were described by Suzuki and Adachi (1991a,
b) and Suzuki and Kato (2008). The interferences were corrected
through the stripping procedure described by Amli and Griffin
(1975). Fluorite, apatite, zircon, monazite, fergusonite, allanite
and thorite which contain detectable amounts of REEs were used as
standards. Some monazite grains were analysed in Canada using a
fully automated JEOL 8200 electron microprobe at Dalhousie Uni-
versity. It is equipped with five wavelength spectrometers, oper-
ating in wavelength-dispersion mode, 15 kV accelerating voltage,
20 nA beam current, 1 mm beam diameter, 20 s peak count-time,
and 10 s background count-time. Both WDS and EDS modes were
used in analysis. Pure rare earth metal standards were used in the
353
analysis of REE group, as well as monazite, almandine, sanidine and
kaersutite mineral standards for the rest of elements. Ilmenite,
rutile and the other Fe-Ti oxides were analysed in Sweden using
Cameca BX50 electron microprobe analyser equipped with three
spectrometers and a back-scattered electron detector (BSE). The
operating conditions were 20 kV acceleration voltage, 12 nA beam
current, and 1 mm beam diameter. The analysis was performed
under an acceleration voltage of 15 kV, a sample current of
0.045e0.5/JA, and an electron-beam diameter of ~2/urn. Each
mineral grain was analysed three times and their averages were
taken.
The major and selected trace element for the bulk sandstone
samples were analysed at the Cement Factory in Kirkuk City (Iraq).
The sandstones were crushed to small pieces using a jaw crusher
and then powdered using a corundum ball mill. Loss on ignition
(LOI) was determined by heating the dried samples up to 950  C for
two hours. The powdered sample were mixed (1:10) with a 2:1
mixture of lithium tetraborate (Li2B4O7) and lithium metaborate
(LiBO2) to prepare fusion discs. The major and trace element ana-
lyses were determined on fusion discs by Rigaku type X-ray fluo-
rescence spectrometer (XRF) using a wavelength-dispersive setting
under the following operational conditions: 35 mA current, 40 kV
voltage, PET and LiF200 crystals. The standard reference material
SRM 1887a (portland cement) obtained from the National Institute
of Standards & Technology (USA) was used for accuracy and pre-
cision measurements. The precision was obtained by taking the
average of ten times repeated analysis of the standard. The accuracy
was ±1% (relative) for SiO2, ±2% for the other major oxides, and ±5%
(relative) for both minor oxides and trace elements.
The radioactivity of sandstones were detected during the field
work using Geiger counter (GR110), while the sources of radioac-
tivity were detected by using red cellulose nitrate films fixed on
polished and polished thin sections prepared from rocks and heavy
minerals. The cellulose nitrate films are 12 mm thick, sensitive to
alpha particles with <4 MeV energy, and are affected by beta rays,
gamma rays, and ordinary light.
4. Results
4.1. Petrography of Amij Formation
The clastic part of the Amij Formation consists of kaolinite,
mixed illite-montmorillonite and illite claystones alternating with
sandstones and marlstones. The sandstones are fine to very fine
grained, mostly of quartzarenite, Fe-sand and sublitharenite types,
dominated by quartz with very minor amounts of feldspars,
muscovite and lithics, and variable amounts of heavy minerals. The
composition of these sandstones is given in Table 1 and Fig. 4. These
detrital grains are cemented mostly by sparry calcite and in fewer
cases by ferruginous or siliceous cement. Some sandstones are very
poorly cemented with clay matrix which is reflected in the highly
friable nature of these rocks (Al-Amiri, 1988). Heavy minerals are
particularly enriched in some uppermost horizons classifying them
as black sandstones; however such horizons are of limited thick-
ness and lateral extent.
The quartz grains of the Amij sandstones are subangular to
subrounded in shape, monocrystalline and contain inclusions of
zircon, tourmaline and rutile; few quartz grains show wavy ex-
tinctions. The feldspars are minor in amount ranging between 1.3
and 2.5% and consist mostly of orthoclase and less commonly of
plagioclase. Muscovite flakes exist in few samples in very minor
amounts. Lithics are very rare reflecting the mature nature of these
sandstones.
The Amij sandstones are of three types, qaurtzarenite, Fe-sand
and sublitharenite based on the geochemical classification
354 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

Table 1
Major (wt.%) and trace element (ppm) composition of the sandstones of Amij Formation.

Sample Major element oxides (%) Total Trace elements (ppm) Log(SiO2 Log(Fe2O3 Sandstone
no. %
SiO2 Al2O3 Fe2O3T CaO MgO TiO2 Na2O K2O SO3 LOI Zr Mn Cr Sr /Al2O3) /K2O) Type

17/2B 95.42 0.37 1.79 0.07 0.03 0.40 0.09 0.28 >0.07 0.54 99.06 682 38 116 37 2.41 0.81 Quartzarenite
17/3 85.67 1.24 2.27 1.95 0.31 2.51 0.02 0.63 >0.07 3.89 98.56 2581 244 460 201 1.84 0.56 Quartzarenite
17/4 89.28 3.17 2.01 0.25 0.24 1.84 0.02 0.53 0.15 1.57 99.08 2434 208 402 275 1.45 0.69 Fe-sand
17/5 89.52 4.46 2.29 0.11 0.08 1.56 0.01 0.41 0.13 1.01 99.58 2087 157 313 159 1.30 0.58 Fe-sand
17/9 87.84 6.02 1.84 0.17 0.07 1.68 0.10 0.33 0.22 0.98 99.25 3109 186 394 266 1.16 0.75 Fe-sand
17/10 78.56 4.19 5.28 3.57 0.37 2.26 0.03 0.73 0.11 4.02 99.12 4395 399 693 517 1.27 0.86 Fe-sand
17/12 90.12 2.95 1.82 0.23 0.21 1.92 0.02 0.50 0.09 1.29 98.86 2276 175 367 356 1.48 0.56 Sublitharenite
17/13 94.60 1.33 0.95 0.43 0.03 1.05 0.04 0.31 0.08 0.57 99.82 1300 76 187 131 1.85 0.49 Quartzarenite
17/15 94.07 3.14 0.35 0.08 0.02 0.74 0.03 0.35 0.10 0.91 99.79 1236 64 130 153 1.47 0.00 Sublitharenite
17/16 58.26 5.36 1.83 0.18 7.24 0.56 0.31 0.27 0.18 15.52 99.71 675 n.d. 152 27 1.04 0.83 Fe-sand
124/2 95.68 0.79 0.56 0.28 0.19 0.68 0.04 0.24 >0.07 0.76 99.29 1088 58 94 61 2.08 0.37 Quartzarenite
124/3 96.35 0.40 0.74 0.12 0.09 0.54 0.02 0.27 >0.07 0.35 99.95 744 28 295 55 2.38 0.44 Quartzarenite
124/6 93.76 0.77 1.34 0.62 0.16 1.17 0.07 0.45 >0.07 0.91 98.41 1411 165 315 180 2.08 0.70 Quartzarenite
124/7 88.14 1.55 3.20 1.38 0.26 2.79 0.06 0.77 0.08 1.74 99.97 1366 157 401 241 1.75 0.51 Quartzarenite
124/11 85.53 0.80 4.91 1.83 0.37 3.00 0.41 1.30 >0.07 1.05 98.22 1997 191 142 175 2.20 0.58 Quartzarenite
124/15 94.11 2.78 0.85 0.20 0.05 0.74 0.02 0.52 0.10 0.46 99.83 874 65 160 44 1.53 0.21 Sublitharenite
124/16 62.07 7.00 1.54 8.85 5.11 0.52 0.44 0.18 0.27 14.1 100.10 975 82 136 39 0.95 0.93 Fe-sand
410/3 94.16 1.79 1.01 0.22 0.05 1.16 0.07 0.34 >0.07 0.67 99.54 4728 265 564 198 1.72 0.47 Quartzarenite
410/6 86.79 0.84 3.17 2.86 0.36 1.82 0.06 0.66 >0.07 2.49 99.12 2768 219 496 151 2.01 0.68 Quartzarenite
410/8 96.68 0.39 0.64 0.17 0.01 0.63 0.02 0.24 >0.07 0.39 99.24 829 69 228 128 2.39 0.43 Quartzarenite
410/9 93.15 2.41 0.91 0.16 0.04 0.82 0.05 0.15 >0.07 1.28 99.04 1563 170 366 68 1.59 0.78 Quartzarenite
410/14 82.94 1.02 2.06 4.17 0.42 1.75 0.02 0.57 0.07 5.84 98.86 3680 182 383 461 1.91 0.56 Quartzarenite
410/15 80.89 3.17 6.45 0.84 0.07 4.63 0.05 0.67 0.07 1.13 98.97 5046 570 973 197 1.4 0.98 Fe-sand
410/17 83.30 7.64 1.51 0.56 0.34 0.91 0.07 0.43 0.11 3.47 98.34 4437 141 297 178 1.03 0.55 Sublitharenite
410/18 94.55 0.46 2.63 0.11 0.03 0.99 0.08 0.24 0.13 0.85 100.07 986 72 159 154 2.31 1.04 Quartzarenite
410/19 60.26 6.35 1.17 9.53 6.05 0.48 0.28 0.44 >0.07 14.50 99.13 873 47 167 18 0.98 0.42 Sublitharenite
607/3 77.94 0.63 5.24 3.29 0.97 4.05 0.08 0.61 >0.07 4.14 97.02 4934 420 847 256 2.09 0.93 Quartzarenite
607/7 81.15 0.38 4.37 2.08 0.75 3.14 0.11 0.52 0.20 5.01 98.71 4940 315 707 311 2.33 0.92 Quartzarenite
607/8 91.68 2.75 1.24 0.53 0.07 1.56 0.06 0.37 0.15 0.92 99.33 1922 159 379 203 1.52 0.53 Sublitharenite
607/12 49.74 1.96 17.36 0.17 0.85 8.48 0.27 0.60 0.21 9.79 99.43 29,105 2700 5733 1395 1.40 1.46 Fe-sand
607/13 85.28 0.71 3.62 2.84 0.44 1.47 0.07 0.47 >0.07 3.55 98.52 3192 180 421 313 2.08 0.89 Quartzarenite
607/15 90.68 2.89 1.75 0.67 0.20 1.18 0.02 0.33 >0.07 0.88 99.67 2004 103 290 165 1.50 0.72 Fe-sand
607/16 58.96 4.85 0.91 11.35 7.49 0.75 0.16 0.40 0.19 15.18 100.24 547 37 222 24 1.25 0.36 Sublitharenite
Mean 89.87 0.93 2.32 1.33 0.27 1.65 0.08 0.47 0.11 2.00 99.02 2282 168 364 184 2.06 0.66 Quartzarenites
Mean 76.32 4.25 4.48 1.65 1.58 2.52 0.14 0.45 0.17 5.44 99.43 5537 551 1010 338 1.27 0.87 Fe-sands
Mean 81.79 4.35 1.12 3.21 2.03 1.01 0.09 0.43 0.12 5.25 99.36 1738 98 246 139 1.32 0.38 Sublitharenites

diagram of Herron (1988) (Fig. 4; Table 1). The mean SiO2 (wt %)
content of these sandstones decreases from quartzarenite (89.87 ±
6.01; n ¼ 17), to sublitharenite (81.78 ± 15.58; n ¼ 7) to Fe-sand
(76.32 ± 15.58; n ¼ 9). The Al2O3 content is relatively low in
quartzarenite (0.93 ± 0.57), while it is relatively high in sub-
litharenite (4.35 ± 1.98) and Fe-sand (4.25 ± 1.64). The Fe2O3T
content is relatively high in Fe-sand (4.48 ± 5.14) and relatively low
in quartzarenite (1.32 ± 1.58) and sublitharenite (1.12 ± 0.48). The
TiO2 content is relatively high in the three rock types and reaches
8.48% in the Fe-sand (Table 1). The K2O content is low in all three
rock types ranging between 0.43 and 0.47. Similarly, the MgO, CaO,
and Na2O contents are low in all three rock types. The Fe-sands are
much richer in trace elements (Zr, Mn, Cr, and Sr) than quartz-
arenites which are in turn richer than sublitharenites (Table 1).

4.2. Heavy minerals

Fifty five polished thin sections of the heavy mineral concen-

Fig. 4. Chemical classification of the Amij sandstones based on the log (SiO2/Al2O3) vs.
log (Fe2O3/K2O) diagram of Herron (1988).
trates were prepared and studied under plane polarized light mi-
croscope and 100 grains were counted for each sample using Frantz
point counter (Table 2). The percentage of heavy minerals in the
sandstones of Amij Formation is relatively high compared to that in
other formations exposed in the western desert of Iraq, ranging
between 0.6 and 55.4% with a median value of 3.36%. They exist
either as scattered minerals between sand grains or as distinct
concentrated horizons of black sands along sedimentary structures
such as cross beds. The thickness of these individual black sand
layers reaches 10 cm. The heavy minerals may be sub-divided into
two groups, transparents and opaques (Table 2; Fig. 5). The trans-
parent group may be sub-divided according to Pettijohn et al.
(1973) classification into ultrastable minerals (zircon, tourmaline,
rutile; abbreviated as ZTR), stable (monazite, staurolite, apatite,
garnet) and moderately stable minerals (sphene, kyanite); celestine
which is not listed by Pettijohn et al. (1973) can be placed with the
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 355

Table 2
Heavy minerals (HM) % in the heavy mineral separates from the sandstones of Amij formation.

Number HM%/Rock Opaques% Zircon% Monazite% Rutile% Tourmaline% Others%

1 0.75 56 16 10 8 5 5
2 4.03 67 12 8 6 4 3
3 3.50 65 10 9 7 4 5
4 2.71 59 16 7 8 6 4
5 3.35 66 13 9 7 3 2
6 7.33 71 10 7 3 4 5
7 3.46 58 15 9 9 5 4
8 1.54 66 11 8 6 6 3
9 1.10 55 17 14 9 3 2
10 3.72 58 15 11 11 4 1
11 2.15 65 13 7 6 5 4
12 2.30 63 12 8 8 5 4
13 0.78 72 12 7 5 4 0
14 11.82 59 19 8 7 5 2
15 2.07 65 13 12 6 3 1
16 4.10 73 6 7 7 3 4
17 4.28 64 11 8 6 5 6
18 1.18 65 12 9 8 3 3
19 6.60 56 15 13 9 4 3
20 2.08 70 9 10 6 2 3
21 2.55 72 7 7 9 5 0
22 3.37 67 10 6 6 7 4
23 0.98 71 13 10 2 4 0
24 4.31 63 14 9 5 4 5
25 1.03 63 11 8 9 5 4
26 3.55 55 15 12 6 7 5
27 2.89 69 11 9 6 3 2
28 1.93 72 7 6 5 6 4
29 5.27 54 12 14 9 5 6
30 10.18 62 15 9 8 4 2
31 5.50 65 9 8 7 5 6
32 3.49 58 13 15 10 4 0
33 5.36 65 12 8 7 4 4
34 4.44 67 10 7 6 5 5
35 1.22 76 9 6 4 3 2
36 2.56 68 8 8 9 4 3
37 3.38 63 19 7 5 2 4
38 10.01 73 9 5 6 4 3
39 2.32 64 13 6 10 4 3
40 1.30 57 9 12 9 7 6
41 8.24 68 8 9 7 3 5
42 6.51 70 10 7 5 5 3
43 3.23 65 8 10 8 6 3
44 55.94 72 12 5 6 3 2
45 46.81 71 8 7 5 4 5
46 48.23 75 7 8 5 3 2
47 3.65 66 12 9 7 5 1
48 2.46 58 11 15 9 4 3
49 0.65 55 18 12 8 4 3
50 2.55 65 12 11 7 2 3
51 1.46 57 12 9 11 6 5
52 5.82 69 9 7 8 3 4
53 2.11 72 8 8 6 4 2
54 3.36 70 12 9 7 2 0
55 2.02 63 11 10 10 4 2
Minimum% 0.7 54.0 6.0 5.0 2.0 2.0 0.0
Maximum% 55.94 76 19 15 11 7 6
Average% 6.1 65.0 11.7 8.9 7.1 4.2 3.2
Median% 3.36 65 12 8 7 4 3

unstable minerals (Table 2; Fig. 5a). Meanwhile the opaques can be
sub-divided into Fe-Ti oxides (ilmenite, pseudorutile, pseudorutile-
rutile, leucoxene), Fe-oxides and hydroxides (magnetite, hematite,
goethite) and chromite (Table 3; Fig. 5b). The opaques are more
dominant than the transparent grains with a median of 65% of the
total heavy minerals; while the transparent minerals form 35%
including 23% of ultrastable (ZTR) and 12% of the less stable min-
erals. The median percentage of Fe-Ti oxides, Fe-oxides and chro-
mite relative to the total opaque minerals are 51%, 46.5% and 2%,
respectively (Table 3). The median values of the most abundant
heavy minerals relative to the percentage of heavy minerals in
sandstones are: opaques (65%), zircon (12%), monazite (8%), rutile
(7%), tourmaline (4%) and others (3%) (Table 2). The median values
of individual opaques relative to the opaque minerals group in their
order of abundance are: pseudorutile (42.5%), goethite (26.5%),
hematite (9.5%), magnetite (8%), leucoxene (6%), ilmenite (2.5%),
and chromite (2%) (Table 3).
356 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

Fig. 5. Pie diagrams showing the relative percentages of heavy minerals in the heavy mineral fraction within the sandstones of Amij Formation (a); and the relative percentages of
opaque minerals within the opaque mineral fractions (b) which form the major part of total heavy minerals shown in (a).

4.3. Autoradiography
Red cellulose films (LR115 type-II) were used to investigate the
source of radioactivity in the sandstones of Amij Formation. These
films are sensitive to alpha particles emitted by U and Th (Michel,
1984) which exist within the structure of some heavy minerals.
The films were fixed on polished thin and polished sections of the
whole samples as well as on the pure single mineral mounts of
monazite and zircon which were expected to be the source of
radioactivity. They were left in a dark box for two months and then
treated with 10% potassium hydroxide solution in a water bath for
one hour as recommended by Kleeman and Lovering (1967). The
spontaneous radioactive damage from the heavy minerals is re-
flected as mirror image of the fission tracks on the cellulose films
(Basham and Easterbrook, 1977). The results showed that the
source of radioactivity was from monazite and zircon grains. It was
also noticed that the purple coloured zircon grains were more
radioactive than the yellow and colorless ones which was indicated
from the intensity of fission tracks left over the cellulose films. Al-
Amiri (1988) concluded in similar study that in addition to zircon as
the main source of radioactivity, some of the radioactivity was also
coming from the cementing material; however, the cement source
was not detected in our study in spite of leaving some films
attached to polished sections for three months duration.
4.4. Optical and physical properties of monazite
Monazite in the sandstones of Amij Formation was identified
optically and by EPMA techniques. Other than the biaxial figure of
monazite and the dominant dark amber yellow color, it can be
confused with the yellow coloured zircon grains when they coexist.
It is not easy to obtain perfect and easily recognizable optical figure
for heavy minerals because of their small grain size. For this reason,
it may have been confused with zircon by previous researches such
as Al-Amiri (1988) and Al-Salihi (1989). Unlike zircon, monazite is
soluble in hot concentrated sulphuric acid (Deer et al., 1972a, b).
The monazites of Amij Formation are dark amber yellow or purple
red, semi-transparent in color with distinct pleochroism, rounded
to subrounded in shape, mostly of silt size, rarely contain fluid in-
clusions and lack zoning. The surface of monazite grains are pitted
which is the result of weathering and erosion since it has a mod-
erate resistance to such conditions. It showed high radioactivity
attributed to its high content of Th and U indicated by high con-
centration of fission tracks left over the sensitive cellulose films.

Table 3
Opaque mineral counts in the sandstones of Amij Formation. Sample numbers are those used in Table 2a.

Sample. No. Fe-Ti oxides% Fe-oxides% Chromite%

Pseudorutile and rutile-pseudorutile Leucoxene Ilmenite Total Magnetite Hematite Goethite Total

2 33 3 2 38 12 15 33 60 2
6 40 6 2 48 8 11 30 49 3
10 48 4 3 55 6 16 23 45 0
16 46 4 2 52 7 10 28 45 3
22 39 6 1 46 8 11 32 51 3
33 45 6 3 54 9 16 20 45 1
38 57 8 3 68 5 7 18 30 2
42 38 7 4 49 8 9 32 49 2
45 52 5 2 59 7 10 23 40 1
48 40 7 3 50 10 13 25 48 2
Minimum 33 3 1 38 5 7 18 30 0
Maximum 57 8 4 68 12 16 33 60 3
Median 42.5 6 2.5 51 8 9.5 26.5 46.5 2
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 357

Table 4
Crystal chemistry of Amij monazites based on EPMA.

Oxide % 1 2 3 4 5 6 7 8 9 10 11 12 13

P2O5 28.16 27.37 30.00 29.24 29.90 30.22 29.24 28.87 29.75 27.75 30.22 27.36 29.01
SiO2 1.33 2.02 0.33 0.72 0.76 0.44 0.89 1.05 0.37 0.84 0.30 1.93 0.94
Sub-total 29.49 29.39 30.33 29.96 30.66 30.66 30.13 29.91 30.12 28.58 30.51 29.29 29.95
ThO2 10.50 9.17 7.69 5.31 10.68 4.59 11.23 5.24 9.33 2.75 7.19 9.21 11.58
UO2 1.05 0.82 1.77 0.63 0.64 0.40 0.34 0.41 1.09 0.03 2.24 0.94 0.44
Sub-total 11.54 9.99 9.46 5.94 11.32 4.99 11.56 5.65 10.41 2.78 9.43 10.14 12.02
Y2O3 0.66 2.64 1.55 1.26 2.84 3.21 2.56 0.06 1.28 0.71 3.11 1.37 2.22
La2O3 13.92 11.76 16.99 12.26 12.82 12.40 10.23 16.68 10.67 16.51 10.38 13.16 7.90
Ce2O3 27.01 25.63 26.77 26.71 24.60 26.04 24.09 29.81 25.47 31.83 22.92 27.07 23.30
Pr2O3 2.53 2.90 2.11 3.15 2.48 2.94 2.66 2.68 3.00 2.85 2.83 2.66 3.00
Nd2O3 8.56 10.66 7.13 12.02 8.92 11.87 10.48 10.70 11.45 10.04 10.93 10.00 13.40
Sm2O3 1.37 2.32 0.92 2.42 1.57 2.26 2.16 1.18 1.99 0.98 2.03 1.62 1.85
Eu2O3 0.72 0.72 0.61 0.88 0.67 0.90 0.75 0.79 0.70 0.85 0.67 0.75 0.85
Gd2O3 1.04 1.61 0.78 2.00 1.25 2.05 1.71 0.38 1.15 0.58 2.11 0.82 1.33
Dy2O3 0.29 0.75 0.40 0.58 0.63 0.91 0.69 0.00 0.30 0.16 0.80 0.38 0.57
Ho2O3 0.00 0.00 0.00 0.05 0.00 0.04 0.05 0.00 0.00 0.00 0.19 0.00 0.00
Er2O3 0.00 0.08 0.00 0.00 0.16 0.19 0.11 0.00 0.00 0.10 0.05 0.07 0.21
Yb2O3 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Sub-total 56.09 59.06 57.26 61.35 55.99 62.79 55.49 62.28 56.01 64.62 56.02 57.90 54.61
CaO 1.45 0.45 1.83 0.81 1.95 0.75 1.88 0.50 2.11 0.42 1.91 0.53 1.96
FeOt 0.00 0.00 0.00 0.00 0.02 0.00 0.01 0.03 0.00 2.69 0.00 0.00 0.01
Sub-total 1.45 0.45 1.83 0.81 1.97 0.75 1.88 0.53 2.11 3.10 1.91 0.53 1.97
Total % 98.58 98.89 98.89 98.05 99.93 99.19 99.06 98.37 98.65 99.08 97.87 97.87 98.55
SREE % 55.44 56.43 55.71 60.08 53.15 59.58 52.93 62.21 54.73 63.90 52.91 56.53 52.39
Eu/Eu* 1.85 1.14 2.19 1.23 1.46 1.27 1.19 3.59 1.40 3.41 0.99 1.98 1.65
(La/Sm)N 6.34 3.16 11.50 3.15 5.08 3.41 2.95 8.77 3.33 10.47 3.18 5.05 2.66
(La/Nd)N 3.13 2.12 4.59 1.97 2.77 2.01 1.88 3.00 1.80 3.17 1.83 2.54 1.14
Structural formula based on 16 oxygens
P 1.910 1.858 1.989 1.970 1.960 1.991 1.943 1.946 1.986 1.882 2.006 1.875 1.945
Si 0.106 0.162 0.026 0.057 0.059 0.034 0.070 0.083 0.029 0.067 0.023 0.157 0.074
Sum T- sites 2.016 2.021 2.015 2.028 2.019 2.025 2.013 2.029 2.015 1.949 2.029 2.031 2.019
Th 0.191 0.167 0.137 0.096 0.188 0.081 0.201 0.095 0.167 0.050 0.128 0.170 0.209
U 0.019 0.015 0.031 0.011 0.011 0.007 0.006 0.007 0.019 0.000 0.039 0.017 0.008
Sum A4þ sites 0.212 0.182 0.170 0.107 0.202 0.088 0.214 0.107 0.186 0.051 0.167 0.186 0.216
Y 0.028 0.113 0.065 0.053 0.117 0.133 0.107 0.003 0.054 0.030 0.130 0.059 0.093
La 0.411 0.348 0.491 0.360 0.366 0.356 0.296 0.490 0.310 0.488 0.300 0.393 0.231
Ce 0.792 0.753 0.768 0.778 0.697 0.742 0.692 0.869 0.735 0.934 0.658 0.802 0.675
Pr 0.074 0.085 0.060 0.091 0.070 0.083 0.076 0.078 0.086 0.083 0.081 0.078 0.087
Nd 0.245 0.305 0.200 0.342 0.247 0.330 0.294 0.304 0.322 0.287 0.306 0.289 0.379
Sm 0.038 0.064 0.025 0.066 0.042 0.061 0.058 0.032 0.054 0.027 0.055 0.045 0.050
Eu 0.020 0.020 0.016 0.024 0.018 0.024 0.020 0.021 0.019 0.023 0.018 0.021 0.023
Gd 0.028 0.043 0.020 0.053 0.032 0.053 0.045 0.010 0.030 0.015 0.055 0.022 0.035
Dy 0.007 0.019 0.010 0.015 0.016 0.023 0.017 0.000 0.008 0.004 0.020 0.010 0.015
Ho 0.000 0.000 0.000 0.001 0.000 0.001 0.001 0.000 0.000 0.000 0.005 0.000 0.000
Er 0.000 0.002 0.000 0.000 0.004 0.005 0.003 0.000 0.000 0.002 0.001 0.002 0.005
Yb 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Sum A3þ sites 1.643 1.751 1.654 1.784 1.610 1.810 1.610 1.807 1.618 1.895 1.629 1.721 1.593
Ca 0.125 0.039 0.154 0.069 0.162 0.063 0.158 0.043 0.178 0.036 0.160 0.046 0.166
Fe 0.000 0.000 0.000 0.000 0.001 0.000 0.000 0.002 0.000 0.180 0.000 0.000 0.001
Sum A2þ sites 0.125 0.039 0.154 0.069 0.163 0.063 0.158 0.045 0.178 0.216 0.160 0.046 0.167
Sum all cations 3.995 3.993 3.993 3.988 3.994 3.986 3.996 3.988 3.997 4.111 3.986 3.985 3.995
End members End-members %
Monazite % 85.57 94.30 83.13 91.50 82.10 92.20 82.40 94.08 80.84 95.02 82.36 93.45 81.56
Cheralite % 12.97 4.19 15.47 7.07 16.48 6.37 16.17 4.46 17.76 3.57 16.22 5.03 17.01
Huttonite % 1.46 1.51 1.41 1.44 1.43 1.43 1.43 1.46 1.40 1.40 1.42 1.52 1.43

Structural formula (Ce0.39Nd0.16La0.18Pr0.04Sm0.02Gd0.02Eu0.01Y0.04Th0.05U0.01Ca0.04Fe0.00)(P0.98Si0.03)O4

Eu-anomaly ¼ Eu/Eu* ¼ Eucn/√[Smcnx Gdcn] (McLennan, 1989); Chondrite normalization values are after Taylor & McLennan, 1985); nd ¼ not determined.

Monazite is also paramagnetic due to REEs and Y content which
helped in separating its grains from the rest of accompanying heavy
minerals by isodynamic magnetic separator. During separation,
monazite grains were shifting towards the magnetic side under 0.7
A current, and front and side inclination angles of 15 and 20 ,
respectively. Few grains of tourmaline, pink zircon and opaque
minerals were also separating with the dominant monazite grains
under these conditions; however, pure monazite grains were ob-
tained by repeated trials under the same conditions and finally by
hand picking under binocular microscope. Monazite forms 5e15%
with a median of 8% from the heavy minerals (Table 2; Fig. 5a).
4.5. Crystal chemistry of monazite
Monazite has a complex geochemistry because of the variable
nature of the elements accommodated into its structure and the
variation in their concentrations and substitutions. Its general for-
mula can be expressed as (REE)PO4 (Huminicki and Hawthorne,
358 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

14 15 16 17 18 19 20 21 22 23 24 25 Min. Max. Mean Median

29.32 30.07 29.91 30.11 30.07 29.50 29.15 29.26 30.14 28.38 30.65 29.16 27.36 30.65 29.31 29.32
0.86 0.34 0.42 nd 0.12 0.37 1.08 0.09 0.13 0.40 nd 0.26 0.09 2.02 0.69 0.44
30.18 30.41 30.33 30.11 30.19 29.87 30.23 29.35 30.27 28.78 30.65 29.42 27.45 32.67 30.01 30.12
9.23 7.05 3.47 3.57 3.06 4.31 4.56 5.65 4.29 4.80 5.81 4.65 2.75 11.58 6.60 5.65
1.09 2.17 0.31 0.51 0.37 1.06 0.64 0.52 0.42 0.54 0.33 0.30 0.03 2.24 0.76 0.54
10.32 9.22 3.78 4.08 3.43 5.37 5.20 6.17 4.71 5.34 6.14 4.95 2.78 13.82 7.36 6.14
1.54 3.38 2.34 2.83 1.57 2.89 2.55 2.41 1.45 1.81 0.65 1.14 0.06 3.38 1.92 1.81
13.70 11.87 12.15 12.45 11.77 13.15 12.94 12.88 12.56 15.85 14.25 12.34 7.90 16.99 12.86 12.56
25.13 23.34 29.54 28.66 29.00 26.84 27.03 27.70 28.51 29.11 27.32 29.17 22.92 31.83 26.90 27.01
2.58 2.59 3.20 3.21 2.81 2.86 2.51 2.84 1.73 1.87 2.41 2.29 1.73 3.21 2.67 2.68
8.86 9.84 12.27 13.38 15.74 12.36 14.00 13.61 16.11 9.84 15.00 14.06 7.13 16.11 11.65 11.45
1.72 1.86 1.80 1.55 1.69 1.88 2.41 1.50 1.20 0.95 0.77 2.85 0.77 2.85 1.71 1.72
0.75 0.66 nd nd nd nd nd nd nd nd nd nd 0.61 0.90 0.75 0.75
1.20 1.86 1.66 1.20 0.93 1.73 1.11 0.88 1.09 1.55 0.92 1.43 0.38 2.11 1.29 1.20
0.68 0.89 nd nd nd nd nd nd nd nd nd nd 0.00 0.91 0.32 0.58
0.00 0.18 nd nd nd nd nd nd nd nd nd nd 0.00 0.19 0.02 0.00
0.00 0.15 nd nd nd nd nd nd nd nd nd nd 0.00 0.21 0.04 0.07
0.00 0.00 nd nd nd nd nd nd nd nd nd nd 0.00 0.05 0.00 0.00
56.16 56.61 62.96 63.28 63.51 61.71 62.55 61.82 62.65 60.98 61.32 63.28 40.88 78.73 59.85 61.32
1.74 1.80 0.94 0.79 0.58 1.04 0.33 0.47 0.09 2.41 nd 0.55 0.09 2.41 1.14 0.87
0.01 0.00 0.20 0.17 0.31 0.11 0.01 0.38 0.00 0.00 0.22 0.13 0.00 2.69 0.17 0.01
1.75 1.80 1.14 0.96 0.89 1.15 0.34 0.85 0.09 2.41 0.22 0.68 0.09 5.10 1.31 1.14
98.41 98.04 98.21 98.43 98.02 98.10 98.32 98.19 97.72 97.51 98.33 98.33 97.51 99.93 98.53 98.33
54.63 53.23 60.62 60.45 61.94 58.82 60.00 59.41 61.20 59.17 60.67 62.14 52.39 63.90 57.93 59.17
1.61 1.08 nd nd nd nd nd nd nd nd nd nd 0.99 3.59 1.74 1.46
4.96 3.97 4.20 5.00 4.33 4.35 3.34 5.34 6.51 10.38 11.52 2.69 2.66 11.52 5.43 4.35
2.98 2.32 1.91 1.79 1.44 2.05 1.78 1.82 1.50 3.10 1.83 1.69 1.14 4.59 2.25 1.97
Structural formula based on 16 oxygens
1.959 1.996 1.987 1.965 2.010 1.975 1.949 1.981 2.025 1.929 1.986 1.977 1.858 2.025 1.960 1.970
0.068 0.027 0.033 0.077 0.009 0.029 0.085 0.007 0.010 0.032 0.077 0.021 0.007 0.162 0.057 0.057
2.027 2.023 2.020 2.042 2.020 2.004 2.035 1.988 2.036 1.961 2.062 1.997 1.949 2.062 2.017 2.020
0.166 0.126 0.062 0.063 0.055 0.078 0.082 0.103 0.077 0.088 0.101 0.085 0.050 0.209 0.119 0.101
0.019 0.038 0.005 0.009 0.007 0.019 0.011 0.009 0.007 0.010 0.006 0.005 0.000 0.039 0.013 0.010
0.188 0.165 0.067 0.071 0.061 0.096 0.093 0.112 0.085 0.097 0.107 0.090 0.051 0.216 0.133 0.107
0.065 0.141 0.098 0.116 0.066 0.122 0.107 0.103 0.061 0.077 0.026 0.049 0.003 0.141 0.081 0.077
0.399 0.343 0.352 0.354 0.343 0.384 0.377 0.380 0.368 0.469 0.402 0.364 0.231 0.491 0.375 0.366
0.726 0.670 0.849 0.809 0.838 0.777 0.782 0.811 0.828 0.856 0.765 0.855 0.658 0.934 0.779 0.778
0.074 0.074 0.092 0.090 0.081 0.082 0.072 0.083 0.050 0.055 0.067 0.067 0.050 0.092 0.077 0.078
0.250 0.275 0.344 0.368 0.444 0.349 0.395 0.389 0.457 0.282 0.410 0.402 0.200 0.457 0.329 0.322
0.047 0.050 0.049 0.041 0.046 0.051 0.066 0.041 0.033 0.026 0.020 0.079 0.020 0.079 0.047 0.047
0.020 0.018 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.024 0.012 0.018
0.031 0.048 0.043 0.031 0.024 0.045 0.029 0.023 0.029 0.041 0.023 0.038 0.010 0.055 0.034 0.031
0.017 0.023 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.023 0.008 0.008
0.000 0.004 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.001 0.001
0.000 0.004 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.005 0.001 0.000
0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.000
1.629 1.651 1.826 1.809 1.842 1.810 1.828 1.829 1.826 1.807 1.715 1.854 1.593 1.895 1.742 1.784
0.147 0.151 0.079 0.065 0.049 0.088 0.028 0.040 0.008 0.207 0.082 0.047 0.008 0.207 0.096 0.079
0.001 0.000 0.013 0.011 0.021 0.007 0.001 0.025 0.000 0.000 0.014 0.009 0.000 0.180 0.011 0.001
0.148 0.151 0.092 0.076 0.070 0.095 0.029 0.066 0.008 0.207 0.096 0.056 0.008 0.387 0.107 0.095
3.992 3.989 4.006 3.999 3.993 4.006 3.984 3.995 3.954 4.073 3.980 3.997 3.954 4.111 3.999 3.993
End-members %
83.49 83.35 90.75 91.95 93.59 89.86 95.61 94.40 97.68 80.32 89.93 93.81 80.32 97.68 88.93 90.75
15.08 15.24 7.86 6.63 4.99 8.75 2.92 4.16 0.82 18.43 8.60 4.78 0.82 18.43 9.64 7.86
1.43 1.41 1.39 1.42 1.42 1.39 1.46 1.44 1.50 1.24 1.47 1.42 1.24 1.52 1.43 1.43

2002), or more specifically as (Ce,La,Nd,Th)PO4 (Nickel and
Mandarino, 1987; Mange and Morton, 2007). Four varieties of
monazite are known (Linthout, 2007). These types are monazite-
(Ce) (Nickel and Mandarino, 1987), monazite-(La) (Levinson, 1966),
monazite-(Nd) (Graeser and Schwander, 1987), and monazite-(Sm)
(Masau et al., 2002).
EPMA-WDS analyses for the major and minor elements for
25 monazite grains of the Amij Formation showed that its
average median composition consists predominantly of REE-
oxides (59.17%) and P2O5 (29.32%), with lesser amounts of
ThO2 (5.65%), UO2 (0.54%), Y2O3 (1.81%), CaO (0.87%), SiO2
(0.44%), and FeOt (0.01%) (Table 4). The REE-oxides form the
major part of this composition ranging between 52.39 and
63.90% including Ce2O3 (26.90%), Nd2O3 (11.65%), La2O3
(12.86%), Pr2O3 (2.67%), Sm2O3 (1.71%), Gd2O3 (1.29%), Eu2O3
(0.75%), Dy2O3 (0.32%), Er2O3 (0.045%), Ho2O3 (0.02%), and
Yb2O3 (0.002%). Ce, Nd, and La are the dominant LREEs where
the amount of Ce (0.78 apfu) is more than twice the combined
amount of Nd (0.33 apfu) and La (0.37 apfu) (Fig. 6a). The Amij
monazite is highly depleted in HREE accounting for only 0.65%
of the total REE%. Based on the median values of the structural
formula units (apfu) (Table 4), the elemental concentrations in
Amij monazite arranged in decreasing order are P > Ce > La >
Nd > Th > Ca > Pr > Y > Si > Sm > Gd > Eu > U > Dy > Ho > Fe
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 359

Fig. 6. Ternary diagrams applied to the monazites from the black sandstones of Amij Formation (this study) with comparative examples from Saudi Arabia, namely Al-Wajh black
sands, northwestern Arabian Shield on the Red Sea (from Moufti, 2009) and from Jabal Al-Massah granitoids at the extreme northwestern part of the Arabian Shield near the border
with Sinai Peninsula (from Bakhsh, 2013): (a) Ternary diagram between the dominant three LREEs: La2O3-Ce2O3-Nd2O3 in the structure of monazite; (b) Nomenclature diagram for
the system 2REEPO4 e CaTh(PO4)2 - 2ThSiO4, the new tripartite division for the system monazite e cheralite e huttonite of Linthout (2007).

> Er > Yb. The average formula of monazite based on the me-
dian values of cations per 16 atoms of oxygen is (Ce0.39
Nd0.16La0.18Pr0.04Sm0.02Gd0.02Eu0.01Y0$04Th0$05U0$01Ca0$04Fe0.00)
(P0$98Si0.03)O4. This composition shows that the monazite of
Amij Formation is classified as monazite-(Ce) type (Linthout,
2007; Nickel and Mandarino, 1987) (Fig. 6b). Microprobe
elemental maps indicate homogenous distribution of elements
with no signs of zoning in the monazite grains (Fig. 7).
The compositional variations can also be explained in terms of
ionic substitution which is governed by the effective ionic size and
charge factors. These compositional variations are controlled by the
substitution of LREE by a number of elements, particularly Th, U, Y,
Ca, Si, and HREE. These substitutions are explained by cheralite-
coupled substitution (2REE3þ / (Th,U)4þ þ Ca2þ) and huttonite-
coupled substitution (REE3þ þ P5þ / (Th,U)4þ þ Si4þ) reactions
(Linthout, 2007; Harlov et al., 2007; Dawood and Abd El-Nabi,
2007; Zhu and O’Nions, 1999a; Van Emden et al., 1997). The
uncoupled substitution of Y / REE also takes place in monazite
(Spear and Pyle, 2002).
Correlation coefficients (Table 5) and bivariant diagrams (Figs. 8
and 9) of Amij monazites show that the ƩREE have no correlation
with P; but negative correlations with Th, U, Si, Ca, and Y. The
perfect negative correlation (r ¼
0.99) between these two groups
of elements; i.e., (ƩREE þ P) vs. (Th þ U þ Si þ Ca þ Y) is a clear
indication of the coupled and uncoupled substitutions taking place
in the structure of monazite (Fig. 8a). Substitutions of ƩREEþ3 by

Fig. 7. Electron microprobe BSE image for a group of monazite grains from Amij Formation. (upper left) and X-ray elemental maps for O, P, Ce, La, Nd, Th, U, Gd, Yb, Mo, and Ca.
360 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

Table 5
Crystal chemistry of Amij zircons based on EPMA.

Oxide % Z1 Z2 Z3 Z4 Z5 Z6 Z7 Z8 Z9 Z10 Z11 Z12 Range Mean

SiO2 31.40 30.07 30.25 30.90 29.50 29.94 31.54 30.28 30.46 31.05 30.70 31.27 29.50e31.54 30.61
ZrO2 60.34 59.12 55.18 60.72 58.16 57.26 60.07 56.72 57.03 55.34 56.33 54.63 54.63e60.72 57.58
HfO2 2.93 6.05 7.69 4.05 8.35 9.31 6.15 8.58 7.85 8.19 7.95 7.26 2.93e9.31 7.03
Y2O3 0.75 2.11 2.64 1.82 1.64 1.70 0.30 2.04 2.06 2.38 2.44 4.65 0.30e4.65 2.04
ThO2 0.54 0.47 1.56 0.45 0.52 0.33 0.51 0.35 0.60 0.66 0.41 0.37 0.33e1.56 0.56
UO2 0.23 0.17 0.41 0.12 0.18 0.09 0.17 0.10 0.18 0.31 0.15 0.11 0.09e0.41 0.19
Al2O3 0.21 0.23 0.15 0.30 0.11 0.02 0.03 0.25 0.20 0.18 0.20 0.35 0.02e0.35 0.19
Total % 98.40 98.22 97.89 98.36 98.47 98.65 98.77 98.32 98.38 98.11 98.18 98.64 97.89e98.77 98.37
Structural formula based on 4 Oxygens
Si 1.0083 0.9745 0.9941 0.9856 0.9660 0.9779 1.0033 0.9859 0.9891 1.0083 0.9968 1.0081 0.9660e1.0083 0.9915
Zr 0.9448 0.9342 0.8842 0.9444 0.9287 0.9120 0.9318 0.9005 0.9031 0.8763 0.8918 0.8588 0.8588e0.9448 0.9093
Hf 0.0269 0.0560 0.0721 0.0369 0.0780 0.0868 0.0558 0.0797 0.0728 0.0759 0.0737 0.0668 0.0269e0.0650 0.0650
Y 0.0113 0.0321 0.0408 0.0273 0.0252 0.0261 0.0045 0.0312 0.0314 0.0363 0.0372 0.0704 0.0045e0.0311 0.0311
Th 0.0039 0.0035 0.0117 0.0033 0.0039 0.0025 0.0037 0.0026 0.0044 0.0049 0.0030 0.0027 0.0025e0.0117 0.0042
U 0.0016 0.0012 0.0030 0.0009 0.0013 0.0007 0.0012 0.0007 0.0013 0.0022 0.0011 0.0008 0.0007e0.0030 0.0013
Al 0.0079 0.0088 0.0058 0.0113 0.0042 0.0008 0.0011 0.0096 0.0077 0.0069 0.0077 0.0133 0.0008e0.0133 0.0071
Total Cations 2.0048 2.0102 2.0116 2.0096 2.0074 2.0067 2.0014 2.0102 2.0098 2.0108 2.0112 2.0209 2.0014e2.0209 2.0095
Hf# 2.76 5.65 7.54 3.76 7.75 8.69 5.65 8.13 7.46 7.97 7.63 7.22 2.76e8.59 6.67
Zr/Hf 20.59 9.77 7.18 14.99 6.97 6.15 9.77 6.61 7.26 6.76 7.09 7.52 6.15e20.59 9.22
ThO2/UO2 2.35 2.76 3.80 3.75 2.89 3.67 3.00 3.50 3.33 2.13 2.73 3.36 2.13e3.80 3.11

Thþ4, Uþ4, Siþ4, Caþ2 and Yþ3 are indicated by negative correlations
with Th þ U (r ¼
0.93) (Fig. 8b), Ca þ Si (r ¼
0.80) (Fig. 8c), and Y
(r ¼
0.43) (Fig. 8d). The negative correlation between ƩREE vs. (Th
þ U þ Ca) (r ¼
0.95) (Fig. 8e) and ƩREE þ P with (Th þ U þ Ca) (r ¼

0.96) (Fig. 8f) reflects cheralite coupled substitution; while the
strong negative correlation between ƩREE vs. (Th þ U þ Si) (r ¼

0.89) (Fig. 8g), and ƩREE þ P vs. (Th þ U þ Si) (R ¼
0.94) (Fig. 8h)
supports huttonite coupled-substitution (Gagne et al., 2009;
Linthout, 2007; Harlov et al., 2007; Dawood and Abd El-Nabi,
2007; Zhu and O’Nions, 1999a; Van Emden et al., 1997). There is
no correlation between ƩREE and P (r ¼ þ0.03) (Fig. 8i) which are
the two dominant group of elements in monazite composition
indicating that there is no substitution between them. The negative
correlation of ƩREE and Y (r ¼
0.43) (Fig. 8d) suggests uncoupled-
substitution (Spear and Pyle, 2002). The positive correlation be-
tween Fe with ƩREE (r ¼ þ0.52) (Fig. 8j) suggests that Fe is not
substituting for REE.
The cheralite-type substitution is also supported by the positive
correlations between Ca and (Th þ U) (r ¼ þ0.81) (Fig. 9a), and Ca
and (Th þ U þ Ca) (r ¼ þ0.92) (Fig. 9b); meanwhile the huttonite-
type substitution is also indicated by positive correlation between
Si and (Th þ U) (r ¼ þ0.43) (Fig. 9c), and Si and (Th þ U þ Si) (r ¼
þ0.56) (Fig. 9d). The positive correlation between Ca þ Si and Th þ
U (r ¼ þ0.88) (Fig. 9e) further shows the absence of substitution
between these elements as a support that these four elements are
partially replacing the ƩREE (Fig. 8b, c) and P (Fig. 9g). The negative
correlation between Y with ƩREE (r ¼
0.61) (Fig. 8d) and positive
correlation with P (r ¼ þ0.57) (Fig. 9g) indicates that Y is
substituting REE rather than P. Fe is showing positive correlation
with P (r ¼ þ0.35) (Fig. 9f) and negative correlation with Y (r ¼

0.49) (Fig. 9i), and Ca þ Si (r ¼
0.68) (Fig. 9j) indicating that Fe is
not substituting for P but rather for Ca, Si, and possibly Y.
4.6. REE patterns
The Amij monazite like other monazites worldwide is rich in
LREE and poor in HREE which were mostly below their detection
limits (Fig. 10a, b; Table 4). The REE distribution pattern shows a
small positive Eu anomaly (Eu/Eu*, where Eu* ¼ [(Sm)CN x
(Gd)CN]½) ranging between 0.99 and 3.59 with an average of 1.74
and median 1.46; and a strong Pr anomaly (Pr/Pr*, where Pr* ¼
[(Ce)CN x (Nd)CN]½)) ranging between 8.45 and 10.77 with an
average of 9.13. The (La/Sm)CN and (La/Nd)CN ratios range between
2.66 ─ 11.52 and 1.14 ─ 4.59 with average and median values of 5.43
and 4.35, and 2.25 and 1.97, respectively (Table 4).
4.7. Correlation coefficients
Pearson’s correlation coefficient application on the chemical
analysis results of Amij monazite (Table 5) showed some significant
positive and negative correlations supporting the bivariant re-
lations shown in Figs. 8 and 9. REEs show significant positive cor-
relation with LREEs (La, Ce, Nd) and Fe, and significant negative
correlation with the HREEs (Dy, Ho, Er), Eu, Th, U, Y, and Ca. With
few exceptions, most HREEs show significant positive correlations
between themselves; meanwhile most of the LREEs show signifi-
cant negative correlations between themselves. Ce and Nd which
are the dominant REE with La show significant negative correlation
with Th, U, Y, and Ca. P show significant negative correlation with Si.
Th show significant positive correlation with Ca, Er, Dy, and Eu. U
show significant positive correlation with Ca, Ho, and Dy. Y has
significant positive correlation with HREEs (Er, Ho, Dy, Gd) and Sm.
4.8. Other heavy minerals
Other than monazite which is the main investigated heavy
mineral in Amij sandstones, some other abundant minerals
including zircon, and Fe-Ti minerals group are also described in
some detail including their chemistry and other characteristics
with brief description of the other minerals which are mostly minor
in occurrence.
1. Zircon
Like monazite, zircon is considered one of the most important
heavy mineral. This is because of its content of economically
important elements such as Zr, Hf, and U-Th. In addition to its
economic value, zircon is one of the most widely studied and
indispensible mineral in geochronological, gemological, prove-
nance and many other studies.
The zircon percentage relative to total heavy minerals in Amij
sandstones range between 6 and 19% with a median of 12%
(Table 2). Zircon grains are mostly colorless and some have pale
yellow or pale pink color. Two populations of zircon were
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 361

Fig. 8. Bivariant correlation diagrams showing negative correlations reflecting the coupled substitutions in monazite (a) to (h), and positive correlations (i) and (j). (a)
(ƩREE2O3þP2O5) vs. (ThO2þUO2þSiO2þCaO þ Y2O3) (r ¼
0.99); (b) ƩREE2O3 vs. (ThO2þUO2) (r ¼
0.53); (c) ƩREE2O3 vs. (CaO þ SiO2) (r ¼
0.55); (d) ƩREE2O3 vs. Y2O3
(r ¼
0.61); (e) (ƩREE2O3) vs. (ThO2þUO2þCaO) (r ¼
0.74); (f) (ƩREE2O3þP2O5) vs. (ThO2þUO2þCaO) (r ¼
0.82); (g) (ƩREE2O3) vs. (ThO2þUO2þSiO2) (r ¼
0.58); (h)
(ƩREE2O3þP2O5) vs. (ThO2þUO2þSiO2) (r ¼
0.60); (i) ƩREE2O3 vs. P2O5 (r ¼ þ0.44); (j) ƩREE2O3 vs. Fe2O3 (r ¼ þ0.13).
362 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

Fig. 9. Bivariant correlation diagrams showing dominant substitution relations between elements constituting the Amij monazites. (a) CaO vs. (ThO2þUO2) (r ¼ þ0.12); (b) CaO vs.
(ThO2þUO2þCaO) (r ¼ þ0.67); (c) SiO2 vs. (ThO2þUO2) (r ¼ þ0.11); (d) SiO2 vs. (ThO2þUO2þSiO2) (r ¼ þ0.43); (e) (CaO þ SiO2) vs. (ThO2þUO2) (r ¼ þ0.19); (f) Fe2O3 vs. P2O5
(r ¼ þ0.31); (g) (CaO þ SiO2) vs. P2O5 (r ¼
0.74); (h) Y2O3 vs. P2O5 (r ¼
0.27); (i) Fe2O3 vs. Y2O5 (r ¼
0.42); (j) CaO þ SiO2 vs. Fe2O3 (r ¼
0.75).

recognized, the more abundant euhedral, elongate with or without Zircon was separated on the non-magnetic side of the isodynamic
bipyramidal endings, zoned and rich in inclusions; and the less magnetic separator at 1.7 A current, front and side inclination an-
abundant smaller, rounded and devoid of zoning and inclusions. gles of 15 and 3 , respectively. EPMA of the major elements in 12
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 363

2. Rutile

Rutile forms 7% median value of the heavy minerals in Amij

sandstones with an range of 2e11% (Table 2). In addition to TiO2
which form 98.04% in average with a range of 92.77e99.66% of the
composition of 20 analysed grains, rutile contains minor amounts
of FeO (0.47%), SiO2 (0.18%), Al2O3 (0.23%), CaO (0.38%), MgO
(0.02%), K2O (0.01%), Na2O (0.01%), Cr2O3 (0.33%), and MnO (0.01%)
(Table 6). They exist as dark reddish brown or light yellowish or-
ange grains. The dark grains are elongate with sharp edges or
rounded pleochroic with an average size of 75 mm; meanwhile the
more abundant light coloured grains are elongate, larger in size
(100 mm) and occasionally contain inclusions of smaller rutiles. It
was separated on the non-magnetic side of the Isodynamic mag-
netic separator at 0.7 A current and front and side inclinations
angles of 15 and 5 , respectively (Tables 7 and 8).

3. Tourmaline

Tourmaline exists in considerable amounts with a median value

of 4% and a range of 2e7% of the heavy minerals (Table 2; Fig. 5a).
Tourmaline grains which are mostly dravites show either elongate
or rounded outlines and have a variety of colours.

4. Ti-Fe oxides

This group forms 51% of opaque heavy minerals with a range of

Fig. 10. (a) Chondrite-normalized REE patterns of Amij monazite for the minimum,
maximum and median concentrations of ten analyses shown in Table 3. The Eu/Eu*
values are given in Table 3. Eu/Eu* is calculated as EuCN/√(SmCN  GdCN) from
McLennan (1989). (b) SmCN vs. (La/Sm)CN ratio diagram shows the degree of frac-
tionation of LREEs. Chondrite values used for normalization are those of Taylor and
McLennan (1985).
zircon grains showed variable ranges and averages because of the
variable types of zircons within the Amij Formation (Table 5). The
mean formula of the studied zircons is (Zr0.909Hf
0.065Th0$004U0$001Y0.031)S1.011(Si3$966Al0.028)S0.999O4. The low Zr in
these zircons compared to standard zircon (ZrSiO4) is due to sub-
stitutions by Hf, Th, U, and Y as it is clear from the formula. The
atomic ratio 100(Hf/(Hf þ Zr) of Amij zircons range between 2.76
and 8.59, placing them within the range of zircon proper based on
the nomenclature for natural zircon (e.g., Fleischer, 1955; Neves and
Nunes, 1974).
38e68% and comprise ilmenite which is the primary mineral and
its alteration products, pseudorutile, pseudorutile-rutile and leu-
coxene (Table 3).
Ilmenite which is the primary source of most of the secondary
Ti-Fe oxides form 2.5% of the opaques with a range of 1e4%
(Table 6; Fig. 5b). The chemical analysis of 13 ilmenite grains
showed that it consists of 54.97% TiO2 (50.33e57.81%) and 40.89%
FeOt (28.49e44.63%) and minor amounts of SiO2 (0.33%), Al2O3
(0.21%), CaO (0.32%), MgO (0.39%), and MnO (2.61%) (Table 6). It has
a pale pinkish color under reflected polarized light with abundant
exsolution lamellae. The average formula of these ilmenites is
Ti1$04Fe0$87Mn0$06O3.
Pseudorutile is the most abundant opaque mineral with a me-
dian value of 43.2% and a range of 33e57% (Table 3; Fig. 5b). It has a
bluish grey color and show pleochroism and red internal reflections
under reflected polarized light. The grains are rounded and char-
acterized by vertical cracks to their outer rims due to contraction of
the original ilmenite from which they were derived by alteration. It
was separated at the magnetic side of the isodynamic magnetic
separator under 0.3e0.4 A current and side and front inclinations
angles of 15 and 25 , respectively. Chemical analysis of 22 grains of

Table 6
Summary of chemical analysis of pseudorutile, pseudorutile-rutile, rutile, and ilmenite.

Oxide; Mineral<

Pseudorutile (n ¼ 22) Pseudorutile-rutile (n ¼ 10) Rutile (n ¼ 20) Ilmenite (n ¼ 13)

Min. Max. Mean Min. Max. Mean Min. Max. Mean Min. Max. Mean

TiO2 61.21 66.65 63.73 72.05 83.15 77.14 92.77 99.66 98.04 50.33 57.81 54.97
FeOt 29.20 36.67 33.35 12.33 25.24 18.9 0.01 1.63 0.47 28.49 44.63 40.89
SiO2 0.01 0.44 0.15 0.23 1.67 0.76 0.01 1.46 0.18 0.05 1.23 0.33
Al2O3 0.03 0.58 0.24 0.28 1.74 0.81 0.02 1.64 0.23 0.06 0.54 0.21
CaO 0.08 0.41 0.39 0.33 0.77 0.45 0.21 0.96 0.38 0.09 0.63 0.32
MgO 0.02 2.44 0.28 0.02 0.35 0.11 0.01 0.18 0.02 0.02 2.28 0.39
K2O nd nd nd nd nd nd 0.01 0.03 0.01 nd nd nd
Na2O nd nd nd 0.02 0.11 0.03 0.01 0.09 0.01 nd nd nd
MnO 0.23 3.88 1.49 0.16 3.46 1.03 0.01 0.04 0.01 0.24 12.79 2.61
Cr2O3 0.01 0.14 0.02 0.03 1.47 0.29 0.01 2.86 0.33 nd nd nd
Total % 90.79 111.21 99.65 85.45 117.96 99.52 93.07 108.55 99.68 79.28 119.91 99.72
364 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

pseudorutile showed that it consists dominantly of TiO2 (63.73% in

SREE2O3

1
average with a range of 61.21e66.65%) and FeOt (33.35% in average
and a range of 29.2e36.67%) with minor amounts of SiO2 (0.15%),
Al2O3 (0.24%), CaO (0.39%), MgO (0.28%), MnO (1.49%), and Cr2O3
(0.02%) (Table 6). The average formula of pseudorutile is
0.44*
1
FeOt

Ti2$46Fe1$43Mn0$07O9.
In addition to pseudorutile, another group of Ti-Fe oxides was

0.76**

1

0.28

also recognized as alteration product of ilmenite informally named

CaO

here as pseudorutile-rutile which form a relatively distinct

composition. Based on the analysis of 10 grains, the chemical

0.28

0.06
0.25
Yb2O3

composition of this group consists of 77.14% TiO2 (72.05e83.15%)

and 18.90% FeOt (12.33e25.24%) and minor amounts of SiO2
(0.76%), Al2O3 (0.81%), CaO (0.45%), MgO (0.11%), Na2O (0.03%), MnO
1

0.48*
0.08
0.28
0.36

(1.03%), and Cr2O3 (0.29%) (Table 6).

Er2O3

Leucoxene which is also an alteration product of ilmenite form

6% with a range of 3e8% of opaques (Table 3; Fig. 5b). Its grains have
1

0.43*

0.13
0.32

0.08
0.31
Ho2O3

greyish white to yellowish white color under the reflected polar-

ized light. Most of leucoxene seem to have been formed as alter-
ation products of ilmenite but other source minerals such as
1

0.21

0.19

0.72**

0.46*

0.69**
0.59**

titanomagnetite are also possible.

Dy2O3

5. Fe oxides and hydroxides

1

0.35

0.36
0.034

0.02
0.31
Gd2O3

0.59**
0.55**

The Fe oxides are very abundant in Amij sandstones forming

**Correlation is significant at the 0.01 level (0.5─1.0).The positive and negative correlations are shown in bold and bold italics, respectively.

46.5% of the opaques (Table 3). They consist of 8% magnetite

(5e12%), 9.5% hematite (7e16%), and 26.5% goethite (18e33%)

0.51**

0.57**

0.77**

1
0.08
0.35
0.12

0.28

0.10
Eu2O3

which is their alteration product (Fig. 5b).

6. Other minerals
Sm2O3

0.62**

1

0.16

0.31

0.01

0.06
0.19
0.25
0.36

0.12

In addition to the above mentioned heavy minerals, there are

many others in minor amounts. Among these minerals is chromite
0.52**

1

0.03

0.024

0.22

0.17

0.51**

0.01

0.18

0.60**

0.64**
Nd2O3

which form 2% of the opaques (Table 3; Fig. 5b) and others in lesser
amounts such as staurolite, apatite, garnet, sphene, kyanite and
authigenically formed celestine.
0.40*

1

0.04
0.15

0.06

0.10
0.20
0.11
0.21
0.25
0.27

0.07
Pr2O3

5. Discussion

0.45*

0.057**
0.91**
0.53**

1

0.21

0.52**

0.56**

0.79**

0.53**

0.37
0.26

0.12

The heavy minerals of the sandstones of Amij Formation are

Ce2O3

dominated by opaques (pseudorutile, pseudorutile-rutile, leucox-

ene, ilmenite, magnetite, hematite, goethite and chromite) (65%),
ultrastable minerals (zircon, tourmaline, rutile) (23%), and meta-
0.48*

0.55**

0.63**

0.63**
1
0.36

0.21

0.00

0.40*

0.32

0.39

0.08

0.37

0.43*
Pearson’s correlation coefficient matrix for 19 variables of 25 monazite grains.

La2O3

stable minerals (monazite, staurolite, sphene, kyanite, apatite,

garnet, and celestite) (12%). This combination of heavy minerals in
the sandstones of Amij Formation indicates igneous-dominated

0.43*

0.28
0.29
0.21

0.51**
0.47*

0.07
0.42*

0.00
0.26

0.56**
0.47*
0.46*
0.68**

source rocks with minor contribution from metamorphic com-

Y2O3

plexes. The source of opaques and ultrastable minerals are most

probably from the basic igneous rocks and granitoids, respectively;
while some of the metastable minerals such as monazite, sphene

0.34

0.62**

0.50*

0.04
0.03

0.30
0.27
0.05

0.48*

0.07

0.61**

0.07
0.34
0.49*
0.70**

and apatite are mostly from the granitoids and others such as
UO2

*Correlation is significant at the 0.05 level (0.4─0.5).

kyanite, staurolite and garnet are of high-grade metamorphic

origin.

0.38

0.86**

0.31

0.08

0.06

0.10

0.51**

0.02

0.73**

0.37
0.07
0.32
0.43*
0.57**

0.60**

0.59**

The Al2O3/TiO2 vs. (SiO2)adj diagram of Le Bas et al. (1986) shows

ThO2

that the source of the sandstones of Amij Formation were felsic

igneous rocks supporting the interpretation that they were derived

0.26

0.03

0.04
0.05
0.26

0.17
0.33

0.12

0.19

0.44*
0.11

0.15
0.00

0.13

0.01
0.55**

0.51**
1

from a granitic-gneissic source area (Fig. 11a). The tectonic indicator

SiO2

diagrams of Roser and Korsch (1986) (Fig. 11b) and Bhatia (1983)
(Fig. 11c) indicates passive margin provenance. The overall petro-
1

0.03
0.29
0.09
0.13

0.07
0.30

0.01
0.25

0.32

0.02
0.36

0.02

0.22

0.21
0.30
0.18

0.24

0.82**

graphic and geochemical results suggest that the Amij sandstones

P2O5

were probably derived from continental areas and were deposited

in a passive margin tectonic setting.
The high resistance of monazite to many geological processes
SREE2O3
Oxides

Sm2O3
Nd2O3
Ho2O3

Gd2O3
Dy2O3
Yb2O3

such as weathering, erosion, sedimentation, and metamorphism

Eu2O3

Ce2O3
La2O3
Er2O3

Pr2O3
Table 7

ThO2
Y2O3

P2O5
FeOt

SiO2
UO2
CaO

makes it one of the common members together with the ultra-

stable minerals in placer deposits (Mariano, 1989; Nagy and
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 365

Table 8
Comparison between the monazite compositions from the black sandstones of Amij Formation (this study), and monazites from black sands of Wadi Thalabah, Al-Wajh area,
NW Arabian Shield on the Red Sea, Saudi Arabia (Moufti, 2009), and monazites from granitoid complexes of Jabal Al-Massah, NW Arabian Shield near the border with Sinai
Peninsula (Bakhsh, 2013).

Rock Type< Black sandstone, Amij formation Black sand Granitoid complex

Area < Wadi Amij, western desert, Iraq Al-Wajh, Saudi Arabia Jabal Al-Massah, Saudi Arabia

Reference< This study Moufti (2009) Bakhsh (2013)

Oxide % ; Minimum Maximum Mean of 25 Median of 25 Monazite-1 Monazite-2 Mean of 2 Minimum Maximum Mean of 10

P2O5 27.36 30.65 29.31 29.32 30.94 28.21 29.58 29.00 33.00 30.50
ThO2 2.75 11.58 6.60 5.65 6.11 8.13 7.12 2.00 4.00 3.29
La2O3 7.90 16.99 12.86 12.56 15.87 19.38 17.63 13.00 19.00 15.20
Ce2O3 22.92 31.83 26.90 27.01 29.43 31.62 30.54 29.00 33.00 31.00
Nd2O3 7.13 16.11 11.65 11.45 12.89 11.55 12.22 8.00 11.00 9.60
Sm2O3 0.77 2.85 1.71 1.72 1.64 1.11 1.38 e e e
Gd2O3 0.38 2.11 1.29 1.20 e e e 2.00 2.00 2.00
CaO 0.09 2.41 1.14 0.87 1.96 e 1.96 0.50 1.00 0.94
SiO2 0.09 2.02 0.69 0.44 e e e 1.00 2.00 1.20
FeOt 0.00 2.69 0.17 0.01 e e e 1.00 1.00 1.00
End-members
Monazite % 80.32 97.68 88.93 90.75 78.26 98.54 88.4 93.12 89.93 91.53
Cheralite % 0.82 18.43 9.64 7.86 20.15 1.00 10.08 5.27 8.52 6.90
Huttonite % 1.24 1.52 1.43 1.43 1.59 1.46 1.53 1.60 1.55 1.57

Draganits, 1999). Monazite forms ~9% of the heavy minerals in
Amij sandstones (Table 2; Fig. 5a). The analysed monazites
showed minor differences in bulk chemistry (Table 4) which is
obvious in their distribution in the triangular composition dia-
grams (Figs. 6a, b) and also in their elemental maps (Fig. 7). The
elemental maps are homogenous and do not show zoning in
monazite grains. The REEs also show minor difference in their
chondrite-normalised distribution patterns with a negative Eu
anomalies (Eu/Eu*) ranging between 0.99 and 3.59 with a me-
dian value of 1.46; the (La/Nd)CN value range between 1.14 and
4.59 with a median of 1.97, while the (La/Sm)CN range between
2.66 and 11.52 with a median of 4.35 (Fig. 10; Table 4). These
curves also show extreme depletion in HREEs relative to LRREs.
The ultrastable heavy minerals and monazite constitute ~32% of
the total heavy minerals (Table 2). All these characteristics sug-
gest that most of these monazites are most probably derived
from granitoids rather than metamorphic rocks because those of
metamorphic origin commonly show various types of zonation
accompanied by compositional variations (Mohr, 1984; DeWolf
et al., 1993; Watt, 1995; Zhu and O’Nions, 1999a, b; Zhu et al.,
1997a, b; Bingen and van Breemen, 1998). The amount of meta-
morphic minerals forms ~3% of the heavy minerals which suggest
minor contribution of the metamorphic rocks as the source of
Amij sandstones.
Monazite occurs in many mineralized areas within the late
Precambrian alkali granites in the northwestern part of Arabian
Shield (Drysdall et al., 1984). These occurrences rich in minerals
containing Nb, Ta, Sn, REE,Y, Th, U, and Zr, are associated with
microgranite, aplite, and pegmatite intrusions of Ghurayyah,
Jabal Sa’id, Umm al Birak and Jabal Hamra (Drysdall et al., 1984)
(Fig. 12). The commonly found heavy minerals in these granitoids
are ilmenorutile, zircon, monazite, bastnaesite, thorite, uraninite,
cassiterite, pyrochlore, xenotime, columbite-tantalite, anatase,
brookite, and others. Similar monazite occurrences were re-
ported in the Neoproterozoic granitoids of Jabal Umm Al Suqian,
Ghurayyah and Jabal Hamra within various parts of the Arabian
Shield (Küster, 2009) (Fig. 12). Monazite, zircon, rutile, magnetite
and many other minerals were found within a large pegmatite
body aligned along the margin of Jabal Sayed (Sa’id) granite at
the northern part of the Arabian Shield (Moghazi et al., 2015).
Bakhsh (2013) and Bakhsh and Alderton (2014) studied five
granitoid complexes (Jabal Thalabah, Jabal Khur Dukhan, Jabal
Rydan, Jabal Al-Massah and Jabal az Zuhd) in the Midyan terrain
at the extreme northwestern tip of the Arabian Shield near the
border with Sinai Peninsula and reported the presence of large
amounts of monazite associated with zircon, allanite, apatite,
hematite, magnetite and others in Jabal Al-Massah (Fig. 12). The
locations of these granitoids containing monazite and other
heavy and ore minerals are shown in Fig. 12. A study by Moufti
(2009) on the black sand stream sediments from Al Wajh area
to the northwest of the Arabian Shield on the Red Sea showed
that they contain gold among other heavy minerals (Fig. 12).
These heavy minerals are rich in Fe-Ti oxides and their alteration
products (titanomagnetite, ilmenite, rutile, titanite, goethite-
limonite, pseudobrookite, leucoxene), zircon, biotite with minor
amounts of monazite, thorite, apatite, hornblende, and pyroxene.
Other than hornblende and pyroxene, most of these heavy
minerals exist in the Amij Formation. The absence of hornblende
and pyroxene is expected because they are unstable and cannot
survive long distance movement conditions as it is expected to
be the case from the Arabian Shield to the location of Amij For-
mation, some 600 kms or more apart. Based on Moufti (2009),
the dominant titanomagnetite opaques are of felsic igneous rocks
origin more than the basic ones and the origin of monazite is
granites and pegmatites that are common in DubaeAl Wajh
district of the Arabian Shield. Published chemical analysis for
monazite in the granitoids of the Arabian Shield is scares. The
only available analysis of monazite in granitoids is that of Bakhsh
(2013) as well as few analyses on stream sands of Moufti (2009).
Chemical analysis of two monazite grains from the sediments of
Wadi Thalabah (Moufti, 2009) and ten monazites from Jabal Al-
Massah granitoids (Bakhsh, 2013) showed close similarity and
comparable chemistry with that of the studied Amij monazites
(Table 6; Fig. 5a, b). Monazites of both localities plot in the
middle of the monazites of Amij Formation on the triplots of Ce-
La-Nd (Fig. 5a) and Huttonite-Monazite-Cheralite (Fig. 5b). The
average composition of the Al-Wajh and AL-Massah monazites is
P2O5 (29.57 and 30.5%); Ce2O5 (30.53 and 31%); La2O3 (17.63 and
15.2%); Nd2O3 (12.22 and 9.6%); ThO2 (7.12 and 3.29%); and CaO
(1.96 and 0.94%). End member-calculation based on Linthout
366 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369

comparison strengthen the believe that the Amij monazites and

the associated heavy minerals were most probably derived from
the weathered igneous-metamorphic complexes of Arabian
Shield which are located ±600 km to the south of the study area
(Fig. 12). Monazite is one of the minerals which exhibit wide
range of substitutions between the LREEs in their composition
producing various proportions of end-members. Taking this fact
into consideration, it is not accidental for monazites from three
different rock types separated by 100s of kilometers, such as the
black sandstones of Amij in Iraq, and the black sands of Al-Wajh
and the granitoids of Jabal Al-Massah in the Arabian Shield of
Saudi Arabia to belong to monazite-(Ce) type and have matching
chemical compositions and end-members (Table 6, Figs. 5a, b)
that suggest their common origin. The Arabian Shield and its
counterpart in Africa (the Nubian Shield) are mostly made up of
igneous and metamorphic complexes of Precambrian age
(Aramco Handbook, 1968; Moufti et al., 2013) (Fig. 12). The idea
of the Arabian Shield being the source of the studied Amij For-
mation is also supported by similar conclusions of all previous
studies on heavy minerals in the clastic-dominated Permian and
Mesozoic formations of western desert of Iraq (e.g., Tobia, 1983;
Sadiq, 1985; Mustafa, 1986; Al-Amiri, 1988; Al-Salihi, 1989;
Ismail, 1989, 1996; and others mentioned therein).
Ilmenite is an important heavy mineral in the black sandstones
of Amij Formation; however it only forms 2.5% of the opaques
because it was pervasively altered to secondary Ti-Fe oxides under
different weathering and diagenetic conditions (Gayara and Ismail,
1996). The first stage of alteration is characterized by only minor
changes with the preservation of most of its original properties
where the TiO2 content did not exceed 58%. The second stage of
alteration resulted in the formation of pseudorutile which is an
abundant mineral. Pseudorutile formed by removal of one third of
iron from the structure of ilmenite and the oxidation of the
remaining two thirds to ferric state where the TiO2 content reached
58% according to the equation 3FeTiO3þ2Hþþ½O2
<Fe2Ti3O9þFe2þþH2O (Dimanche and Bertholome, 1976). It is
believed that this stage of ilmenite alteration takes place during
burial of sediments to certain depth (Austin, 1960) and the avail-
ability of oxygen-rich conditions. Such conditions were apparently
available during the deposition of the sandstones of Amij Formation
involving interaction of deltaic and coastal marine environment.
The third stage of ilmenite alteration resulted in the formation of
pseudorutile-rutile where the TiO2 content reaches70e90% and the
optical properties approaches that of rutile but still retains its
opaqueness. During this stage most of the remaining two third of
the iron within the structure of ilmenite is removed under suitable
Eh-pH conditions. The fourth final stage of ilmenite alteration re-
sults in total removal of iron under acidic conditions as a result of
the presence of carbonic or organic acids which leads to the for-
mation of leucoxene.

Fig. 11. The sandstones of Amij Formation plotted on (a) the Al2O3/TiO2 vs. (SiO2)adj
diagram of Le Bas et al. (1986), (b) the (K2O þ Na2O) (wt%) vs SiO2 (wt%) tectonic
discrimination diagram of Bhatia (1983) and Roser and Korsch (1986), and (c) The
6. Conclusions
tectonic setting discrimination diagram of Bhatia (1983), based on (Fe2O3T þ MgO)
wt.% versus (Al2O3/SiO2) relation (PM ¼ Passive Margin; ACM ¼ Active Continental
Margin; CIA ¼ Continental Island Arc; OIA ¼ Oceanic Island Arc). 1. The studied sandstones of Amij Formation contain thin layers of
highly radioactive black sands which are abnormally rich in
heavy minerals dominated by Fe-Ti oxides, ultrastable minerals
(2007) for the mean composition of the monazites of Al-Wajh (zircon, tourmaline, rutile), monazite and minor amounts of
and Jabal Al-Massah show 88.4 and 91.53% monazite, 10.08 and others; the source of radioactivity is monazite and zircon.
6.90% cheralite, and 1.53 and 1.57% huttonite, respectively; if 2. The monazites of Amij Formation are dark amber yellow or
compared with the monazites of Amij, they are of the same type purple red, semi-transparent in color with distinct pleochroism,
and fall within the same range (Table 4; Fig. 5a, b). This rounded to subrounded in shape, mostly of silt size and rarely
 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369 367

Fig. 12. Geologic map of the Middle East (Aramco Handbook, 1968) showing the study area in relation to the Arabian Shield.

contain fluid inclusions; they form 5e15% with a median of 8% 6. Most of the heavy minerals in Amij Formation are comparable
from the heavy minerals. and have similarities with those in the granitoids and sediments
3. The monazites consists predominantly of REE-oxides (60.56%) of the Arabian Shield.
and P2O5 (29.71%), with lesser amounts of ThO2 (4.44%), UO2 7. The Amij sandstones and their heavy minerals were most
(0.47%), Y2O3 (2.08%), CaO (0.58%), SiO2 (0.32%), and Fe2O3 probably derived from felsic-dominated rocks of the Arabian
(0.21%). Shield which were fluvially transported northward to be
4. The elemental concentration in monazite arranged in deposited under passive margin tectonic setting.
decreasing order are P > Ce > Nd > La > Y > Th > Pr > Ca > Sm >
Gd > Si > U > Fe.
Acknowledgments
5. The monazite is classified as monazite-(Ce) type that is enriched
in P and REE whose formula based on cations per 16 atoms of
We thank everybody who helped in this work including Pro-
oxygen can be expressed as: (Ce0.39Nd0.16La0.19Pr0.04Sm
fessor Grant Wach, Dan MacDonald and Gordon Brown at Dal-
0.02Gd0.02Eu0.01Y0.04Th0.06U0.01Ca0.05Fe0.01)(P0.98Si0.03)O4 ¼ (REE,
housie University (Canada) for their help in allowing the use of
Y, Th.,.)PO4.
research microscope, EPMA analysis and polished thin section
preparation, respectively. Our thanks are also due to Professor
368 Y.A. Kettanah, S.A. Ismail / Journal of African Earth Sciences 123 (2016) 350e369
Suzuki of Nagoya University Center for Chronological Research in
Japan for his help in EPMA analysis for monazite. We thank the
reviewers for their constructive comments. Thanks to the author-
ities at Salahaddin and Kirkuk universities (Iraq) for their moral
support and encouragement to publish this work.
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