Ore Geology Reviews 96 (2018) 247–261

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Ore Geology Reviews

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Differentiation of ironstone types by using rare earth elements and yttrium T

geochemistry – A case study from the Bahariya region, Egypt
⁎
A.M. Afifya,b, , M.E. Sanz-Monteroa, J.P. Calvoa
a
Department of Petrology and Geochemistry, Faculty of Geological Sciences, Complutense University, Madrid, C/ José Antonio Nováis, 2, 28040 Madrid, Spain
b
Department of Geology, Faculty of Science, Benha University, 13518 Benha, Egypt

A R T I C LE I N FO A B S T R A C T

Keywords: This paper deals with the geological and geochemical characterization of ironstone deposits encountered in two
Geochemistry different sedimentary successions (upper Cretaceous and lower Cenozoic) in northern Bahariya, Egypt. The
Rare Earth Elements ironstones occur as uneconomic thin bands, lenses and concretionary beds in Cenomanian clastic rocks of the
Yttrium Bahariya Formation and as economic iron ore associated with Eocene carbonate depositional units. The iron-
Ironstone
stones contain similar iron-bearing minerals, mainly goethite and hematite, which display a variety of fabrics,
Bahariya
i.e. concretionary, massive, stromatolitic-like, oolitic, pisolitic, reniform aggregates, boxwork, liesegang, geode-
Egypt
like and brecciated. The iron-rich minerals preferentially replaced and/or cemented the primary and diagenetic
(mainly dolomite) carbonates. Preservation of fabrics, sedimentary structures and thickness of the precursor
carbonates is conspicuous.
Whole-rock composition of the Cretaceous ironstones shows lower Fe2O3 and MnO contents and relative
enrichment in detrital-derived elements, namely Al, Zr and Nb, when compared with the Eocene ironstones, the
latter showing enrichment in Fe, Mn, Si, and Ba oxides as well as Cu, Zn, Ni and Sr trace elements. Total REE
content in the Cretaceous ironstones ranges widely from 70 to 348 ppm whilst the Eocene ironstones show quite
low content, mostly from 1.96 to 31 ppm. Post Archean Australian Shale (PAAS)-normalized patterns of the
upper Cretaceous ironstones display flat REE patterns, with small positive Eu and Pr, slightly negative Y and Ce
anomalies which are close to unity and intermediate Nd concentrations (between 10 and 100 ppm). In contrast,
PAAS-normalized REE + Y patterns of the Eocene ironstones display LREE positive slope with enriched flat
HREE trend as well as negative Ce anomaly, positive Y and Eu anomalies, and low Nd concentration (in general
less than 10 ppm).
Geochemical data along with sedimentary features of the upper Cretaceous and Eocene ironstones in Bahariya
point to different origins in the two ironstone types, the former having been originated diagenetically whereas
the latter were constrained by hydrothermal fluids. A syngenetic marine origin is ruled out for any of the studied
ironstones. Higher amount of detrital derived elements as well as higher REE concentration in the upper
Cretaceous ironstones than in the Eocene ironstones suggest some contribution from the associated clastic se-
diments. The negative Ce anomaly determined in both types indicates anoxic iron-rich solution that passed to
oxidized surface. The presence of positive Y and Eu anomalies in the Eocene ironstones suggests that iron
precipitation was favoured by hydrothermal reducing conditions, when slightly acidic fluids reached oxidizing
alkaline waters.

1. Introduction Thein, 1989; Heikoop et al., 1996; Mücke, 2000; Mücke and Farshad,
2005; Sturesson et al., 2000; Kappler et al., 2005; El Aref et al., 2006a;
Ferruginous chemical sediments, such as ironstone deposits and Loope et al., 2011; Bekker et al., 2010, 2014; Salama et al., 2012, 2013;
banded iron formations (BIFs) are widely used as archives of geo- Baioumy et al., 2013, 2014; Rasmussen et al., 2014; Sun et al., 2015;
chemical proxies (Bau et al., 2014; Hein et al., 2016). The origin of iron and references therein). Ferromanganese minerals can be formed
ore deposits has long been subject of discussion and controversies. through three main genetic processes, i.e. hydrogenetic, hydrothermal
Furthermore, many genetic models have been proposed, opening a wide and diagenetic, and/or a combination of these processes (Hein et al.,
field for contrasting hypotheses (James, 1966; Stanton, 1972; Siehl and 1997) through different temporal and spatial occurrences. Type of

⁎
Corresponding author.
E-mail address: [email protected] (A.M. Afify).

https://doi.org/10.1016/j.oregeorev.2018.04.019
Received 12 June 2017; Received in revised form 16 April 2018; Accepted 19 April 2018
Available online 21 April 2018
0169-1368/ © 2018 Elsevier B.V. All rights reserved.
A.M. Afify et al. Ore Geology Reviews 96 (2018) 247–261

fluids from which ferromanganese minerals were precipitated, i.e., succession in the northern part of the Bahariya Depression of Egypt
marine/seawater, porewater and/or hot fluids are eventually varied (Fig. 1). One ironstone type is hosted in siliciclastic rocks of the Cen-
according to the formation process (Hein et al., 1997; Bau et al., 2014). omanian Bahariya Formation whereas the other type is mainly asso-
Primary deposition with superimposed lateritic weathering and hy- ciated with the Eocene carbonate units (Fig. 1). An integrated approach
drothermal alteration due to heated groundwater has been suggested as using sedimentology and paleoenvironmental analysis of the host rocks
a genetic model for ironstones (e.g., Salama et al., 2012, 2013, 2014). and the associated ironstones was previously achieved (El Aref et al.,
Hydrothermalism and volcanicity are considered the main factors in 1999, 2006a,b; Helba et al., 2001; Tanner and Khalifa, 2010; Salama
controlling the formation of ferromanganese ore deposits and their et al., 2012, 2013, 2014, 2015; Afify et al., 2015a,b, 2016). This paper
associated minerals (e.g. sulfates, quartz and clays) in various geotec- provides additional new insight on the genesis of the ironstones after
tonic settings (Kimberley, 1989, 1994; Sturesson et al., 2000; Hein detailed mineralogical and geochemical investigation with more con-
et al., 2008). Heikoop et al. (1996) reported the formation of iron ooids cern on the rare earth elements and yttrium geochemistry.
in reef areas under the influence of venting of hydrothermal water as-
sociated with volcanic activity. Similarly, hydrothermal solutions pro-
duce iron ooids in areas where erosion of volcanic rocks locally causes 2. Geology of the study area and ironstone sedimentary features
enrichment of the elements needed for ooid formation (Sturesson et al.,
1999). In addition, Kimberley (1989, 1994) documented precipitation The Bahariya Depression is located near the central part of the
of iron from exhalative fluids associated with active faults. Replacement Western Desert of Egypt (Fig. 1). The area is characterized topo-
of carbonates (Kimberley, 1979; Loope et al., 2011; Afify et al., 2015a), graphically by a plateau of karstified Eocene carbonates surrounding
crystallization from precursor iron oxyhydroxide gels (Harder, 1989), the depression. The outcrop succession in the area comprises, from
mechanical accretion of chamositic clay particles (Bhattacharyya and bottom to top, the lower Cenomanian Bahariya Formation, the upper
Kakimoto, 1982; Van Houten and Purucker, 1984), mixed marine/hy- Cenomanian El Heiz Formation, the Campanian El Hefhuf Formation,
drothermal precipitation (Baioumy et al., 2014) and/or precipitation in and the Maastrichtian Khoman Chalk Formation. The upper Cretaceous
shallow marine or submarine environments (Young and Taylor, 1989; formations are unconformably overlain by the Eocene Naqb, Qazzun
Helba et al., 2001; El Aref et al., 2006a,b; Salama et al., 2012, 2013, and El Hamra formations (Fig. 1) and the Oligocene Radwan Formation.
2014, 2015) linked to sedimentary exhalative hydrothermal processes Basaltic to doleritic dykes, sills, laccoliths and lava flows of Miocene age
in tectonically active areas (Rivas-Sánchez et al., 2006; Hein et al., (El-Etr and Moustafa, 1978; Meneisy, 1990) occur in the northern part
2016) are reported as mechanisms of ironstone formation. of the depression (Fig. 1). The Bahariya area was deformed by four
Variations in mineralogy, geochemistry (major, trace and rare earth tectonic phases during the early Mesozoic, late Cretaceous, post-middle
elements and yttrium (REE + Y)) could help in discriminating the Eocene and middle Miocene respectively (Sehim, 1993; Moustafa et al.,
origin of the fluids leading to the formation of ferromanganese deposits. 2003; Afify et al., 2016). Three of these structural phases affected the
Normalized REE + Y distribution patterns of the iron and manganese exposed rock units of Bahariya where the deep seated normal faults that
deposits are considered good proxies for determining fluid composi- resulted from the early Mesozoic deformation phase were reactivated in
tions, the mineralogy of the precursor phases, the depositional en- the late Cretaceous and post Eocene by oblique slip faults and en-
vironments and/or the physical and chemical conditions of miner- echelon folds (Sehim, 1993; Moustafa et al., 2003; Afify et al., 2015b,
alization (Bau and Möller, 1992; Bau, 1996; Bau et al., 1996,2014; 2016).
Owen et al., 1999; Chen et al., 2006; Hein et al., 2016). Likewise, The studied ironstones occur either as thin bands, irregular beds and
REE + Y have been used as geochemical signatures because of their concretions hosted in siliciclastic deposits of the Bahariya Formation
coherent behavior during geochemical processes and because of their throughout the basin (Fig. 2) or as economic iron ore bodies associated
predictable fractionation (Hein et al., 2016). with Eocene rock units in three mine areas that are closely related to
On this basis, comparison of two iron-bearing rock types occurring two fault systems (Fig. 1). A summary of the main features, i.e. oc-
in a same area but formed under different geological conditions and currences, grade, thickness, morphology and distribution, of both ir-
timing offers an opportunity to better understanding the origin of ir- onstone types is shown in Table 1.
onstone deposits. For this purpose, we studied two different ironstone The ironstones hosted in the Cenomanian Bahariya Formation occur
types from the upper Cretaceous – lower Tertiary sedimentary in its lower and upper units, though they are absent in the middle unit
which, unlike the others, do not contain carbonate rocks (Afify et al.,

Fig. 1. Geological map of the northern Bahariya Depression (modified after Said and Issawi, 1964).

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A.M. Afify et al. Ore Geology Reviews 96 (2018) 247–261

2015a). On the basis of sedimentological and mineralogical analyses,

sources of iron and formation of the upper Cretaceous ironstones were
previously described by Mücke and Agthe (1988), El Aref et al. (1999),
Mesaed (2006), Catuneanu et al. (2006), Tanner and Khalifa (2010) and
Afify et al. (2015a). The latter revealed that they show selective re-
placement of iron-rich carbonates (Fe-dolomite, ankerite) that in turn
replaced and/or cemented primary carbonate deposits, i.e. shell frag-
ments, micrite, carbonate grains, calcrete and rhizoliths fabrics (Fig. 2).
On the other hand, the Eocene ironstones occur as economic iron ore
(Fig. 3) that are mainly concentrated in three mines; Ghorabi, El Harra
and El Gedida areas (Fig. 1) (El Akkad and Issawi, 1963; Basta and
Amer, 1969; El Sharkawi et al., 1984; El Aref et al., 1999; Dabous,
2002; El Aref et al., 2006a,b; Baioumy et al., 2013; Salama et al., 2012,
2014, and references therein). Comparison of these economic ironstone
deposits with the Eocene carbonate rocks of the Naqb, Qazzun and
lower Hamra formations revealed similar sequences, bedding struc-
tures, fossil contents and karstic features (Afify et al., 2015b, 2016). The
Eocene ironstones are unconformably overlain by the upper Eocene
glauconitic clay beds (upper Hamra unit; Afify et al., 2016) (Fig. 3). The
ironstones hosted in the Eocene rocks show extensive replacement and
cementation of both the dolostones of the Naqb Formation and the
limestones of the Qazzun and the lower Hamra formations. Dating of
the larger foraminifers from the youngest fossiliferous ironstone beds at
El Gedida mine as early Bartonian gives indication that the replacement
occurred during the Priabonian time, where sea level regression re-
sulted in subaerial exposure that ultimately related to tectonic de-
Fig. 2. Field photos showing variable sedimentary features of the upper formation of the area (Afify et al., 2016). The replacement was most
Cretaceous ironstones within the Bahariya Formation, A. Thin ironstone crusts probably coeval to the pisolitic ironstone formation on the topmost part
within the Cenomanian clastic rocks (height of photo = 2 m). B. Irregular of the ironstone succession at El Gedida area and before the deposition
concretionary ironstone bed. C. Rhizoliths of plant roots mainly replaced by of the glauconitic overburden that was not affected by ironstone mi-
iron oxyhydroxides. neralization (Afify et al., 2016). The Eocene ironstones display a variety
of fabrics, i.e., concretionary, massive, stromatolitic-like, oolitic, piso-
litic, reniform aggregates, boxwork, geode-like and brecciated, that

Table 1
Summary and comparison of the main characteristics (sedimentary features, mineralogy, constraints and origin) of the upper Cretaceous and Eocene ironstones of the
Bahariya region, Egypt.
Features Upper cretaceous ironstones Eocene ironstones

Occurrence and Occurrence in the lower and upper units of the Cenomanian Bahariya Local occurrence related to two major fault systems in the carbonate
extension Formation along the whole depression. Ironstone is absent in sandstones plateau of the northern Bahariya regionThe ironstones mainly replace
of the middle unit carbonate rocks (limestone and dolostone)
Ironstone occurs mainly in permeable carbonate rocks and sedimentary of the Eocene formations
discontinuities
Morphology Thin crusts, irregular beds up to 1 m thick; also, as concretions up to Large bedded and stratiform ironstones reaching up to 13 m in thickness at
40 cm in diameter included in siliciclastic rocks the Ghorabi and El Harra areas, up to 30 m at the El Gedida mine
Ore texture and Massive, concretionary, brecciated, and leisegang-like rings and Preserved textures of skeletal and non-skeletal grains as well as structures
structure bandsMainly replacive textures including fossiliferous carbonate beds, of precursor carbonates, e.g., massive mud-supported, oolitic and
calcrete fabrics stromatolitic fabrics. Pisolitic, box-work and concretionary fabrics are
(rhizoliths, etc.) common
Iron-bearing minerals Goethite, hematite, Fe-dolomite, ankerite and some siderite Goethite, hematite, some jarosite (and pyrite?)
Associated non-iron Pyrolusite, romanechite, todorokite, barite, quartz Quartz, pyrolusite, jacobsite, romanechite, psilomelane, todorokite, barite,
minerals alunite, apatite
Ore grade Low-grade ironstone deposits in siliciclastic sediments High-grade ironstone deposits, especially those of the El Gedida mine. The
ore deposits of the Ghorabi and El Harra areas are of medium grade due to
high quartz content
Mineral paragenesis Subordinate iron oxyhydroxides formed during early diagenetic stages in Ferromanganese minerals formed after or coeval to silicification of the
paleosol horizons. Most iron oxyhydroxides precipitated in telogenetic Eocene carbonates. Sulfate minerals like barite formed after silica and Fe,
stages after replacement of previously formed dolomite and ankerite Mn minerals through fractures and other types of pores
phases
Ore controls Mainly facies control. Selective replacement of carbonates associated Structurally-controlled. Ironstones formed along two major fault systems.
with the siliciclastic rocks. Formation of the ironstones was favoured by This structure was related to the phase rifting and opening of the Gulf of
uplift of the basin during the Late Cretaceous Suez/Red Sea, which was accompanied by magmatic activity
Fluid migration Enhanced by organic matter decomposition and hydrocarbon migration Enhanced by tectonic activity (faulting as structure conduits) and
magmatic activity
Timing Turonian – Santonian uplift of the region Upper Eocene (mostly Priabonian)
Source of iron Dissolution of siderite, pyrite, Fe-dolomite of the Jurassic rocks Hydrothermal iron-rich fluids migrated upwardly through the major fault
(hydrocarbon-source rock) system. These fluids mostly associated with a magmatic activity during
Other possible sources, i.e. iron-bearing minerals of the host rock upper Eocene that was before the main volcanic extrusive activity occurred
during the Oligocene-Miocene in the Bahariya area

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A.M. Afify et al. Ore Geology Reviews 96 (2018) 247–261

determined by XRD analyses using a Philips PW-1710 diffractometer

and a Bruker D8 Advance diffractometer operating under monochro-
matic Cu Kα radiation (λ = 1.54060 Å) at 40kv and 30 mA. Fused discs
from powder samples were prepared for energy dispersive X-ray
fluorescence (ED-XRF) using a Bruker S2 RANGER X-ray fluorescence
spectrometer with X-Flash Silicon Drift Detector to study major and
trace elements geochemistry. Elemental analyses (in wt.%) and che-
mical composition determination of minerals were carried out on
carbon-coated polished thin sections using a JEOL Superprobe JXA
8900-M wavelength dispersive electron microprobe analyzer (WDS-
EMPA) equipped with four crystal spectrometers and beam diameter
between 2 and 5 µm to minimize damage from the electron beam.
Rare earth elements and yttrium (REE + Y) geochemical analyses
were carried out for 24 ironstone samples using inductively coupled
plasma/mass spectrometry (ICP/MS) following an established analy-
tical protocol and using international certified reference material for
quality control. The analysis was achieved after digestion of 0.25 g of
selected sample powder with 2 ml HNO3 in a capped Teflon-lined vessel
and left in an oven for two days and then evaporated to dryness. The
sample was subsequently digested with 2 ml conc. HF in capped Teflon-
vessel for one day in the oven. The solution was evaporated to dryness
and then 1 ml of HClO4 was added, and further diluted with 25 ml of
4% vol of HCl for analysis. The smoothness of a shale normalized
REE + Y pattern is a simple, but reliable criterion to test the quality of a
chemical analysis and to eliminate questionable data sets (Bau et al.,
2014; Hein et al., 2016). Thus, REE + Y patterns (yttrium was inserted
between Dy and Ho according to its ionic radius) are normalized to
post-Archean Australian Shale (PAAS: McLennan, 1989) to detect re-
semblance in the different types of the studied ironstones. The behavior
of yttrium is similar to that of the heavy rare earth elements, especially
the holmium (Ho) (Jochum et al., 1986). Therefore, yttrium and hol-
mium are coupled in many geochemical environments (Bau and Dulski,
1999). Discrimination between light-REE (LREE; La, Ce, Pr, and Nd),
middle-REE (MREE; Eu, Gd, Tb, and Dy), and heavy-REE (HREE; Er,
Tm, Yb, and Lu) is achieved when plotted together with Sm, Ho, and Y
in spidergrams. Different discrimination diagrams are also plotted, e.g.,
Ce/Ce∗ anomaly against Nd concentration and YSN/HoSN values.
Anomalies of Ce, Eu, La, Gd and Y were also calculated. The Eu, Ce, Pr,
Gd and La anomalies, where shale normalized (SN), are calculated as:
Eu/Eu∗ = 2EuSN/(SmSN+GdSN), Ce/Ce∗ = 2CeSN/(LaSN+PrSN),
Pr/Pr∗ = 2PrSN/(CeSN+NdSN), La/La∗ = LaSN/(3PrSN−2NdSN), Gd/
Gd∗ = GdSN/(0.33SmSN + 0.67TbSN) (Taylor and Mclennan, 1985; Bau
and Dulski, 1996).

4. Results
Fig. 3. Field photos showing the sedimentary features and fabrics of the Eocene
ironstones at the mine areas, A-Outcrop view of big ore body of ironstones at
the central part of the El Gedida mine area (See Fig. 1 for mine location).
4.1. Mineralogy and high resolution textural analyses
Outcrop view of the Eocene ironstone succession (I) unconformably overlain by
upper Eocene glauconitic clays (II). C-Close-up view of brecciated goethitic A combination of XRD, SEM/EDX, EMPA and petrographic analyses
ironstone with fractures-filling barite. D. Geodes of goethitic ironstone. E. Box- was applied to clarify the mineralogical history and composition of the
work structures of ironstones. F-Pisolitic ironstone. G-Stromatolitic-like iron- deposits. The mineralogy of the two ironstone types is characterized by
stone. presence of goethite and hematite as the main iron oxyhydroxides, al-
though the iron carbonates siderite, Fe-dolomite and ankerite are
preserve the textures and structures of the carbonate precursors (Afify common in the ironstone bands, lenses and concretions of the Bahariya
et al., 2015b) (Fig. 3). The stromatolitic, ooidal and oncoidal ironstone Formation (Table 1). Subordinate amount of pyrolusite, todorokite,
fabrics were suggested to be of biogenic origin by Salama et al. (2013). psilomelane, iron-rich clays (glauconite and smectite) and barite are
included in the paragenetic sequence of the upper Cretaceous iron-
stones as well (Afify et al., 2015a) (see Table 2 for chemical formulae of
3. Analytical procedures the minerals). The Eocene ironstones show a more complex mineral
paragenesis comprising quartz and subordinate amount of jarosite,
About 220 samples were collected from the host rocks and asso- alunite, barite, pyrolusite, jacobsite, romanechite, psilomelane, todor-
ciated ironstones in both the Bahariya Formation and the Eocene rock okite, apatite, palygorskite and kaolinite (Table 1; see Table 2 for
units. Detailed petrographic, mineralogical and geochemical char- chemical formulae of the minerals) (Salama et al., 2012; Afify et al.,
acterizations were carried out in the different ironstone samples. All of 2015b).
the hard samples were prepared for petrographic studies where 200 The crystal morphologies, texture and distribution of the iron oxy-
thin sections were done. Mineralogy of all collected samples was hydroxides in the two ironstone types were modified depending on the

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Table 2
Main iron and manganese-bearing minerals and their chemical formula (chemical composition of minerals after Deer et al., 1992).
Mineral class Mineral Chemical formula

Iron-bearing minerals Oxides Goethite FeO%OH

Hematite Fe2O3
Silicates Glauconite K Mg (Fe, Al) (SiO3) 6·3H2O
Nontronite Na0.3Fe2((SiAl)4O10)(OH)2·nH2O
Sulfides Pyrite FeS2
Carbonates Siderite FeCO3
Ankerite Ca)Mg, Fe)(CO3) 2
Fe-Dolomite Ca (Mg, Fe) (CO3) 2
Fe-Calcite (Ca, Fe) CO3

Mn-bearing minerals Mn-Oxyhydroxides Pyrolusite MnO2

Manganite MnO%OH
Rhodochrosite MnCO3
Jacobsite Mn(Mg, Fe)2O4
Romanechite ((Ba,H2O)2(Mn+4,Mn+3)5O10)
Psilomelane Ba(Mn2+)(Mn4+)8O16(OH)4
Manjiroite (Na, K)(Mn+4, Mn+2)8O16·n(H2O)
Todorokite (Na, Ca, K, Ba, Sr)1-x(Mn, Mg, Al)6O12·3-4H2O
Birnessite (Na0.3Ca0.1K0.1)(Mn4+,Mn3+)2O4·1.5·H2O
Cryptomelane K(Mn4+,Mn2+)8O16

Fig. 4. Photomicrographs, scanning electron microscopic (SEM) and back-scattered electron (BSE) images of the iron-bearing minerals forming the upper Cretaceous
(A–C) and Eocene (D–I) ironstones. A-Photomicrograph showing pseudomorphs of iron oxyhydroxides after dolomite/ankerite minerals still preserving their rhombic
morphologies. B-SEM image of highly dissolved grey-colored dolomite crystals cemented by white-colored iron oxyhydroxides. C-BSE image of iron oxyhydroxides
forming white-colored spherical crystals after rhombic dolomite/ankerite minerals. Note the grey colored carbonates that are still not replaced by iron. D–F-
Photomicrographs of oolitic (D), fossiliferous (D, E) and stromatolitic-like (F) fabrics of ironstones preserving the skeletal and non-skeletal grains of their carbonatic
precursors. G-Photomicrograph (in reflected light microscope) showing pisolitic fabrics of iron oxyhydroxides forming the ironstones at the topmost part of the
Eocene succession. H, I-SEM images showing pseudomorphs of hematite mostly after pyrite cubic crystals, with few prismatic goethite (white arrows, H).

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A.M. Afify et al. Ore Geology Reviews 96 (2018) 247–261

porosity, discontinuities, open-spaces and textures of the precursors. and 339 ppm maximum values, respectively) (Appendices A, B; sup-
Using polarized-light and scanning electron microscopes, some iron plementary materials). Likewise, the Eocene ironstones show lower
oxyhydroxide cements exhibit primary open-space filling-textures (e.g., content in elements indicative of detrital input, such as Zr (≤78 ppm)
rosette-like, fibro-radiating, zoned-crystals). The iron-bearing minerals and Nb (≤17 ppm) when compared with the upper Cretaceous iron-
replace the carbonates of the Naqb, Qazzun and lower Hamra forma- stones: Zr (≤1065 ppm) and Nb (≤26 ppm).
tions and preserve their main sedimentary features, i.e. lamination, Using electron microprobe (EMPA), slight geochemical differences
oolitic, stromatolitic and fossiliferous fabrics (Afify et al., 2015a,b; arise when the iron-bearing minerals of the two ironstone types are
Afify, 2016). Thus, it is possible to recognize easily the original skele- considered separately. In the upper Cretaceous ironstones, the iron-
tons of nummulites, alveolinids, mollusks, echinoids and ooids as well bearing minerals show the following average content: FeO ≤ 78.0 wt%,
as the former textures of both the Cenomanian and the Eocene host MnO ≤ 2.2 wt%, MgO ≤ 4.8 wt%, CaO ≤ 2.8 wt%, SiO2 ≤ 4.0 wt%,
rocks (Fig. 4). Likewise, dolomite of the Naqb Formation and/or ferroan Al2O3 ≤ 2.0 wt% and P2O5 ≤ 0.6 wt% (Appendix C; Fig. 7). In contrast,
dolomite/ankerite of the Bahariya Formation are present in the two in the iron-bearing minerals of the Eocene ironstones show higher
ironstone types as relics, pseudomorphs, ghosts and/or crystalline content of FeO ≤ 83.0 wt%, MnO ≤ 8.3 wt% and BaO ≤ 10.0 wt%
rhombic aggregates (Fig. 4). Most of the carbonate textures and struc- (Appendix D; Fig. 8). Moreover, the ferromanganese minerals of the
tures have been preserved in the two ironstone types hosted either in Eocene ironstones are enriched in Ba and Mn but with very low Al and
the Cenomanian clastic rocks (Fig. 4A–C) or in the Eocene carbonates K (Appendix D; Fig. 8).
(Fig. 4D–F). Pisolitic fabrics with irregular cortices of iron oxyhydr-
oxides (Fig. 4G) are observed in the topmost part of El Gedida ironstone 4.2.2. Rare earth elements and yttrium geochemistry
succession and the central part of Gabal Ghorabi (Salama et al., 2012, Data of rare earth elements and yttrium from both the Cretaceous
2013, 2014). Chert, formed mainly of quartz is pervasive in some ir- and the Eocene ironstones are shown in Appendices A and B (supple-
onstone facies as both intergranular and intraparticle (Fig. 4D–F) ce- mentary materials) and plotted in Figs. 9–11. All selected samples for
ment and/or replacement. Cementation by quartz was preferential in REE analyses are those with very low or without apatite or any other
the pores created by dissolution of carbonate bioclasts and found as phosphate minerals where the P2O5 content not exceeds 0.5 wt% except
pseudomorphs of dolomite crystals in the coarse-dolomitized and non- three samples that reach up to 0.7 wt% (Appendices A, B; supplemen-
micritic parts (Afify et al., 2015b). Two genetic stages of quartz ce- tary materials). Total REE content in the upper Cretaceous ironstones
mentation/replacement were recorded; i.e., a first phase which is prior shows a wide range from 70 ppm to 348 ppm (Appendix A). In contrast,
or contemporaneous with the iron oxyhydroxide precipitation and a the Eocene ironstones show very low REE content, ranging from
second phase posterior to the main phase of iron oxyhydroxide for- 1.96 ppm to 31 ppm, except for three samples showing 48, 60, 89 ppm
mation (Afify et al., 2015b). Moreover, some hematite was observed to (Appendix B). The silicified Eocene ironstones are depleted in REE
preserve scarce pyrite pseudomorphs at El Gedida area (Fig. 4H and I). showing a range from 1.96 to 6.85 ppm. In both rock types, light rare
In summary, detailed petrographic analysis of the ironstones hosted earth element (LREE) contents are higher than those of the heavy rare
in both the Cenomanian siliciclastic rocks and the Eocene carbonate earth elements (HREE).
deposits led us to conclude that they are mainly post-depositional Rare earth elements and yttrium (REE + Y) geochemical data are
showing selective replacement of carbonate minerals that preserve their normalized to Post Archean Australian Shale (PAAS; McLennan, 1989)
original fabrics especially those of dolomite crystals. (Figs. 9 and 10). The PAAS-normalized REE + Y spidergrams of the
upper Cretaceous ironstones display similar flat REE patterns, with
4.2. Geochemistry slight positive Eu, Pr and slight negative Ce anomalies which are close
to unity (Appendix A; Fig. 9). PAAS-normalized REE + Y data for the
Geochemical data of the studied ironstone samples are presented in Eocene ironstones display an initial drop from La to Ce followed by
Appendices A, B, C and D (supplementary materials) and plotted in LREE positive slope with rise from the Ce minimum to the Eu maximum
Figs. 5–11. These data represent the study of major oxides, trace and and with slight decrease towards a Lu minimum and enriched flat HREE
rare earth elements of the two ironstone types. trend (Fig. 10). When inserted between Dy and Ho, yttrium (Y) shows a
very weak negative anomaly, which approaches the unity in the upper
4.2.1. Major and trace elements geochemistry Cretaceous ironstones (Fig. 9). The REE + Y spidergrams from the Eo-
The whole-rock composition of the upper Cretaceous ironstones cene ironstones show a more pronounced positive Y anomaly, but si-
shows high Fe2O3 content (≤73 wt%), and very low MnO content milar Ce and Eu anomalies than those determined in the upper Cre-
(≤2 wt%) (Appendix A; Fig. 5). In the carbonate-rich ironstone sam- taceous ironstones (Figs. 9 and 10).
ples, CaO and MgO contents reach up to 12% and 8.5% respectively. Following Bau et al. (2014)’s results, discrimination diagrams of Ce/
The studied samples show relative enrichment in elements indicative of Ce∗ vs. Nd concentration and Ce/Ce∗ vs. YSN/HoSN (SN: shale nor-
terrigenous input, i.e. Al2O3 (up to 7.89 wt%), SiO2 (up to 21.8 wt%) malized) were used to distinguish between the different ironstone
and Na2O (up to 7.8 wt%), which reach up even higher content in the types. Using the same diagrams of Bau et al. (2014), the ironstones
clay-rich ironstone crusts (Appendix A, supplementary materials). show negative to no Ce anomaly (Fig. 11). The upper Cretaceous ir-
When compared with the upper Cretaceous ironstones, the whole- onstones show enrichment in Nd concentrations and fall in the
rock compositions of the Eocene ironstones are characterized by higher 10–100 ppm range with positive correlation between Nd concentration
Fe2O3 (≤99.0 wt%) and MnO (up to 8.0 wt%) contents (Appendix B, and Ce/Ce∗ ratio (Fig. 11A). In contrast, the Eocene ironstones are
supplementary materials). The CaO and MgO contents in these rocks characterized by low Nd concentrations ranging between 0.39 and 8.2
are considerably lower than in the upper Cretaceous ironstones. The (less than 10 ppm) (Fig. 11A).
SiO2 content increases in the more porous and fossiliferous facies Regarding the representation of Ce anomaly vs. YSN/HoSN ratio
reaching up to 75.6 wt% where the quartz mineral dominates (Fig. 11B), the upper Cretaceous ironstone samples show negative YSN
(Appendix B; Fig. 6). The Eocene ironstones show very low Al2O3, Na2O values close to unity (YSN/HoSN ≤ 1) whereas, the Eocene ironstones
and K2O content. The phosphorous content (P2O5) in the two ironstone show positive YSN values (YSN/HoSN ≥ 1), especially for the mangani-
types is very low and mostly below detection limit or less than 0.5 wt% ferous and silicified, oolitic ironstones.
(Appendices A, B, supplementary materials).
Trace element composition of the Eocene ironstones shows higher 5. Discussion
content in Zn (≤1138 ppm), Ni (≤719 ppm) and Sr (≤686 ppm) than
that determined in the upper Cretaceous ironstone (112 ppm, 489 ppm The mineralogical and geochemical study of the two ironstone

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Fig. 5. Binary diagrams showing the bivariate relationships of Fe2O3 vs. SiO2+Al2O3 (A), MnO2 vs. SiO2 + Al2O3 (B) and Fe2O3 vs. MnO2 (C), MgO (D), CaO (E), and
vs. Na2O (F) in the ironstones of the Bahariya formation. The values were determined by X-ray fluorescence.

types, which significantly occur in the same stratigraphic succession, mechanisms. Thus, the underlying Bahariya Formation or the Nubia
not only provides useful signatures for discriminating and better un- aquifer (Dabous, 2002; Salama et al., 2012, 2013, 2014), sea water
derstanding processes of ironstone formation but also allows to con- precipitation to hydrothermal exhalites, and/or the surrounding Naqb
clude that epigenetic hydrothermalism does not overprint the rare earth Formation (Baioumy et al., 2013, 2014), iron leached from the over-
element and yttrium content of previously formed ironstones. lying upper Eocene-lower Oligocene glauconitic clays (El Sharkawi
A variety of formation models and iron sources were proposed for et al., 1984; Dabous, 2002) are eventual sources of iron for the Eocene
the two ironstone types occurring in the Bahariya region. With regard deposits.
to the upper Cretaceous ironstones, transformation of ilmenite detrital Based on recent investigations by Afify et al. (2015a) and Afify et al.
grains into rutile (Mücke and Agthe, 1988), pedogenesis (El Aref et al., (2016), two contrasting genetic models, i.e. diagenetically-formed
1999), the alteration and oxidization of glauconite (Mesaed, 2006; versus hydrothermal, are proposed, respectively, for the upper Cretac-
Catuneanu et al., 2006) and/or due to ground water activity, either eous and the Eocene ironstones occurring in the Bahariya Depression
during early diagenesis (Tanner and Khalifa, 2010) or during late di- (Fig. 12). The ironstone bands, lenses and concretions of the Cen-
agenesis (telogenesis) (Afify et al., 2015a), were interpreted as a pos- omanian Bahariya Formation formed by replacement and/or cementa-
sible source of iron through laterization or diagenetic processes. Like- tion of dolomite and ankerite related to the migration of reducing iron-
wise, different genetic mechanisms were proposed for the upper Eocene rich fluids through discontinuities and permeable facies at a basinal
ironstones; i.e., epigenetic, syngenetic-supergenetic, hydrothermal, la- scale (Afify et al., 2015a). Thermal maturity after burial of the silici-
teritic, primary marine and/or mixed hydrogenous-hydrothermal origin clastics of the Bahariya Formation during the late Cretaceous (Metwalli
(El Akkad and Issawi, 1963; Basta and Amer, 1969; El Aref and Lotfy, and Pigott, 2005) probably accounted for the decomposition of organic
1985; El Aref et al., 1999; Helba et al., 2001; Dabous, 2002; El Aref matter and further hydrocarbon migration to the Bahariya Depression,
et al., 2006a,b; Salama et al., 2012, 2013, 2014; Baioumy et al., 2013, which created reducing conditions favorable to bitumen formation and
2014 and references herein). The source of iron for these Cenozoic ir- mobilization of iron-rich fluids (Afify et al., 2015a) in the region via
onstone deposits varies according to the previously described genetic groundwater with CH4 or other hydrocarbons as reducing agents (Parry

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Fig. 6. Binary diagrams showing the bivariate relationships of Fe2O3 vs. SiO2+Al2O3 (A), MnO2 vs. SiO2+Al2O3 (B) and Fe2O3 vs. MnO2 (C), MgO (D), CaO (E), and
vs. Na2O (F) in the different Eocene ironstone types (manganiferous ironstone, oolitic and fossiliferous ironstone, stromatolitic-like ironstone and pisolitic ironstone)
determined by XRF analysis.

et al., 2009; Parry, 2011) and/or organic acids (Chan et al., 2000). The also consistent with the late Eocene – early Oligocene remagnetization
iron-sourcing minerals could belong to the iron-bearing minerals as- event occurred in the Cenomanian rocks (Odah, 2004). The Eocene
sociated with the Cenomanian Bahariya Formation or most likely the ironstone deposits were related to structural traps where hydrothermal
siderite, Fe-dolomite and pyrite of the underlying Jurassic Khatatba reducing iron-rich fluids migrated through major fault systems (Fig. 1).
Formation which is a hydrocarbon-source rock in the north-Western In this setting, the reduced iron-rich fluids mixed with meteoric water
Desert (Rossi et al., 2001, 2002). The Khatatba Formation is also pre- in phreatic zones and a subsequent vadose phase involving preferential
sent in the northern Bahariya Depression as confirmed by Bahariya 1 corrosion of carbonate host rocks by acid reducing fluids and sub-
well in northern Bahariya Depression drilled by Devon Energy Egypt sequent oxidation of ferromanganese minerals under aerobic condi-
Companies (Moustafa et al., 2003). tions.
In contrast, source of iron for the Eocene ironstones was mostly The two differentiated models are supported by both mineralogical
related to deep-seated hydrothermal iron-rich solutions that moved and geochemical evidence. Variations in mineralogy, major oxides and
through major faults (Afify et al., 2015b). The latter postulated that trace elements geochemistry as well as normalized REE distribution
these fluids were prior to the volcanic eruptions, which occurred in patterns of ironstones can be used to interpret the nature and origin of
vicinity of the mine areas during Oligocene-Miocene (Meneisy, 1990). the forming fluids, the composition of the precursor mineral and/or the
The replacement of the Eocene carbonate rock units (Naqb, Qazzun and physical and chemical conditions in which mineralization processes
lower Hamra formations) by iron minerals took place after Bartonian, took place (Sturesson et al., 2000; Mücke and Farshad, 2005; Bau et al.,
most probably during the Priabonian (Afify et al., 2016). This dating is 2014; Hein et al., 2016).

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Fig. 7. Discrimination diagrams showing correlation between major oxides (FeO vs. MnO2 (A), MgO (B), CaO (C), SiO2 (D), Na2O (E), and vs. Al2O3 (F)) in the three
main minerals forming the upper Cretaceous ironstone crusts; values were determined by using electron microprobe analysis.

5.1. Evidence from major and trace elements deposits, which is consistent with a relatively high content in detrital-
derived major elements, i.e. Al2O3, SiO2 and Na2O. These values are in
Altogether, geochemical insight and petrography reflect replace- general higher than those determined in the Eocene ironstones. In the
ment of the primary and/or diagenetic carbonates by iron-bearing mi- latter deposits, iron and manganese oxides and silica are higher than
nerals, i.e., content of MgO and CaO which reaches up to (Appendices those of the upper Cretaceous counterparts, along with a considerably
A, B) is coincident with the occurrence of carbonate relics and/or higher content of Ba, Cu, Zn, Ni and Sr trace elements, suggests that
pseudomorphs supported by the petrographic evidence (Fig. 4) (Afify formation of the Eocene ironstones was enhanced mostly by hydro-
et al., 2015a,b). Relatively high MgO and CaO contents in the upper thermal input (Bekker et al., 2010; Baioumy et al., 2014; Hein et al.,
Cretaceous ironstones (Appendices A, C) are indicative of partial re- 2016) or by accumulation in a marine setting after weathering of older
placement of dolomite and ankerite by iron oxyhydroxides during tel- rocks (Salama et al., 2012). The elemental analyses of iron-bearing
ogenetic stages (Afify et al., 2015a). Regarding the Eocene ironstones minerals for both ironstone types (Appendices C, D) reveal depletion in
(Appendices B, D), lower CaO and MgO contents than in the Cretaceous Al, Si, Na, K and Zn oxides, especially in the Eocene ironstones, which
deposits suggest that replacement by Fe- and Mn-bearing minerals as supports the exclusion of marine and/or terrigenous sources for these
well as cementation by quartz were actually important in the Eocene minerals (Nicholson, 1992; Hein et al., 2008; Bekker et al., 2010).
carbonates.
High trace element content of zirconium which reaches up to
1065 ppm recorded in bulk chemical analyses of the upper Cretaceous 5.2. Discrimination of ironstone types and interpretation based on REE and
ironstone crusts (Appendix A) is mostly attributed to terrigenous deri- Y content
vation and/or large presence of clay minerals in the siliciclastic
Rare earth elements are especially useful in interpreting the origin

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Fig. 8. Correlation between the major oxides (FeO vs. MnO2 (A), MgO (B), CaO (C), SiO2 (D), Na2O (E), and vs. Al2O3 (F)) in the determined ferromanganese minerals
present in the studied Eocene ironstones; values were determined by using electron microprobe analysis.

of the forming fluids as they are not easily fractionated during sedi-
mentation (McLennan, 1989; Bau et al., 1996, 2014; Hein et al., 2016,
and references herein). In addition, Bau et al. (2014) provided diagrams
for discriminating different origins of ironstones based on rare earth
elements and yttrium contents (Fig. 11).
The total REE contents of the upper Cretaceous ironstones
(69.61–348.84 ppm) and Eocene ironstones (1.96–89.45 ppm)
(Appendices A, B) fall within the range of the ferromanganese deposits
of diagenetic origin (110–489 ppm) and hydrothermal origin
(15–149 ppm) reported by Bau et al. (2014) and are significantly lower
than those usually measured in marine ironstones, which usually range
from 1228 to 2282 ppm. Moreover, the marine ferromanganese oxides
typically show positive Ce anomalies, negative YSN values at higher REY
concentrations and higher Nd concentrations (> 100 ppm). Conse-
quently, a seawater (marine) origin for the two ironstone types is ruled
Fig. 9. PAAS-normalized (McLennan, 1989) REE + Y distribution patterns for
the upper Cretaceous ironstones (Gh – Ghorabi area samples, Dist – Gabal El-
out (Fig. 11).
Dist samples, Hr – El Harra area samples). REE concentrations are higher in the upper Cretaceous ironstones
than in the Eocene ironstones, this being indicative of some

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Fig. 10. REE + Y distribution patterns of six types of Eocene ironstones (manganiferous ironstone of Ghorabi and El Harra mines (A), El Gedida manganiferous
ironstone (B), oolitic ironstone (C), Brecciated ironstone (D), stromatolitic-like ironstone (E), and pisolitic, fossiliferous ironstone (F)), PAAS-normalized (McLennan,
1989). (Gh – Ghorabi mine samples, Gd – El Gedida mine samples, Hr – El Harra mine samples).

contribution from the associated siliciclastic sediments during their conditions whilst no depletion or even Ce enrichment occurs in anoxic
formation. Similar REE + Y values were determined in ferromanganese settings. As well, the negative Ce anomalies suggest suboxic conditions
nodules from the Peru Basin that were interpreted as diagenetic (Von wherein aqueous Ce3+ is depleted (Kakuwa and Matsumoto, 2006).
Stackelberg, 1997). These diagenetic Fe–Mn ironstones display negative Thus, the presence of negative Ce anomalies in the two studied iron-
Y anomalies and negative Ce anomalies, which matches well the results stone types is attributed to the mixing of iron-rich reducing fluids with
obtained in the ironstone crusts in the Bahariya Depression, i.e. nega- oxidized meteoric water.
tive Ce anomalies, negative Y anomalies, and intermediate Nd con- The used discrimination diagrams also support diagenetic and hy-
centrations between 10 and 100 ppm. Accordingly, the REE + Y values drothermal origin for the upper Cretaceous and Eocene ironstones, re-
support a diagenetic origin for the iron-bearing minerals, thus con- spectively (Fig. 11). The diagenetic ironstones show negative Y and Ce
firming previous statement by Afify et al. (2015a). anomalies and intermediate Nd concentrations, between 10 and
Variations in Ce are controlled by redox reactions and can be clearly 100 ppm (Bau et al., 2014; Hein et al., 2016). The upper Cretaceous
observed in the aqueous solutions and their precipitates where cerium ironstones do not show large positive Ce or any significant Y anomalies,
has two oxidation states (Bau et al., 1996; Salama et al., 2012 and re- which point to a diagenetic origin from anoxic pore water that moved
ferences therein). The cerium anomaly results from oxidation of Ce3+ to the oxidized surface. This result is consistent with the model pro-
to Ce4+ and subsequent decoupling of Ce from the other REEs due to posed by Afify et al. (2015a) for these crusts after selective replacement
formation of less soluble Ce4+ species and/or preferential adsorption of of carbonate minerals during the Turonian-Santonian uplift of the Ba-
Ce4+ species. In oxidative environments, Ce3+ changes to the less so- hariya area. The geochemical results, mainly Ce and Y obtained from
luble Ce4+ and thus it removes from the solution, resulting in a nega- the upper Cretaceous ironstones provide evidence for basinal flow
tive Ce anomaly relative to its neighbour elements (Bau and Dulski, systems associated with hydrocarbons even though they are not pre-
1996; Bau et al., 1996; Bolhar et al., 2004). The Ce depletion is evident served. The release of iron by migration of reducing fluids is being in-
for the distribution patterns of dissolved rare earth elements under oxic creasingly recognized as an effective mechanism in geologic record

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in the Bahariya Formation was present to its upper part (Afify et al.,
2014). It was interpreted as a result of increasing temperature affecting
the top part of this rock unit where the upper Eocene iron ore deposits
occur. This evolution in clay mineralogy was absent in the Cenomanian
rocks of Gabal El-Dist where the capping Eocene beds of the Naqb
Formation are not replaced by iron (Afify et al., 2014). Nonetheless, this
hydrothermalism was not recorded in the REE + Y data of the asso-
ciated ironstone crusts of the Bahariya Formation.

6. Conclusions

The studied ironstone types show two different models of iron ac-
cumulation in siliciclastic and carbonate rocks under contrasted geo-
tectonic conditions. The upper Cretaceous ironstones are diagenetic in
origin whilst the ironstones hosted in the Eocene formations formed
after Fe, Mn, Si, Ba-rich hydrothermal fluids. The ironstones present in
the Cenomanian siliciclastic rocks of the Bahariya Formation formed
during telogenetic stages after partial or total dissolution of the car-
bonate, and concomitant with iron oxyhydroxide formation by mixing
of the Fe-rich solutions with meteoric oxygenated water. This was fa-
vored by tectonic uplift in the region during the Turonian–Santonian.
The iron-bearing minerals from the Bahariya Formation and the un-
derlying Jurassic formations were the source of iron after organic
matter decomposition and hydrocarbon migration. In contrast, source
of iron for the ironstones hosted in Eocene carbonate rocks was related
to deep-seated iron-rich solutions that moved through major faults.
The two ironstone types show some similarities in major and trace
element contents, which provide evidence for their formation after
carbonate replacement. However, rare earth elements and yttrium
(REE + Y) values point to different genetic ironstone types. The Upper
Cretaceous ironstones display negative Y and Ce anomalies and inter-
mediate Nd concentrations (between 10 and 100 ppm) indicative of
diagenetic origin, whilst the negative Ce anomaly, positive Y and Eu
Fig. 11. A. Graph of Ce/Ce* vs. Nd concentration for the different studied ir-
anomalies, low Nd concentration (mostly less than 10 ppm) and very
onstones in Bahariya area. B. Binary graph of Ce anomaly vs. YSN/HoSN values
low REE concentrations of the Eocene ironstones strongly support a
for the different studied ironstone types (SN: shale normalized). (Ce/
Ce* = 2CeSN/(LaSN+PrSN)). The encircled areas in the graph are from Bau et al. hydrothermal origin. The presence of positive Y anomalies in the
(2014). Eocene ironstones suggests that iron precipitation occurred rapidly and
immediately after reducing, slightly acidic waters reached oxidizing
and alkaline water.
(Rainoldi et al., 2014, and references therein). On the other hand, the
Accordingly, the rare earth elements and yttrium (REE + Y) are
negative Ce anomaly, positive Y and Eu anomalies and the low Nd
good proxies for discriminating the origin of ferromanganese minerals,
concentrations together with low concentrations of REE in the Eocene
even in the case that two different types occur in the same stratigraphic
ironstones suggest a hydrothermal origin for this rock type. These re-
succession, as observed in the Bahariya Depression.
sults are consistent with the model proposed by Afify et al. (2015b,c)
for the Eocene ironstones, which was mainly based on field and pet-
Acknowledgments
rographic observations. The presence of positive Y anomalies in the
Eocene ironstones suggests that precipitation of Fe-Mn minerals oc-
The authors are grateful to the financial support by the Egyptian
curred very rapidly and immediately after reducing, slightly acidic
Government in a full fellowship during the study of the first author at
waters reached more oxidizing and more alkaline water (Bau and
Complutense University of Madrid, Spain. This work is a part of the
Dulski, 1996).
activities of Research Groups BSHC UCM-910404 and BSHC UCM-
The small positive Eu anomaly in the Eocene ironstones could be a
910607. All our gratitude is devoted to Dr. Laura Gonzalez Acebron,
signature inherited from hydrothermal solutions that lost their positive
Maria Belen Muñoz-Garcia and Valle Lopez (Stratigraphy Department,
Eu anomaly because of a relatively high oxygen level. This is supported
Faculty of Geological Sciences, UCM), for their great help during the
by the fact that, in present oceans, high-temperature hydrothermal
research work. Many thanks to Dr. Cecilia Pérez-Soba Aguilar
solutions lose their Eu anomaly within a few hundred meters away from
(Petrology and Geochemistry Department, Faculty of Geological
vent sites due to the rapid oxidation of Eu as a consequence of mixing
Sciences, UCM), for her help and comments on the geochemical studies.
with oxidized seawater (Klinkhammer et al., 1983). The higher Eu
A standing ovation, in no particular order, goes to Xabier Arroyo Rey,
anomaly in the Eocene ironstones than in the Cretaceous ones provides
Isabel Gómez Pinilla, Teresa Benito Criado, Iván Serrano Muñoz, Pedro
evidence that significantly more REE + Y input from hydrothermal
Lozano and Marián Barajas (Faculty of Geology, UCM) for their help in
solutions was involved in the formation of the former deposits.
laboratory studies and mineralogical and geochemical analyses. The
The major faults cutting through the Cenomanian Bahariya
authors are indebted to Franco Pirajno (Editor-In-Chief of Ore Geology
Formation and the Eocene carbonate rock units act as a conduit for the
Reviews) and İlkay Kuscu (Associate Editor of Ore Geology Reviews) for
hydrothermal solutions during the upper Eocene. The Bahariya
reviewing and editing of the manuscript. We are so grateful to the re-
Formation was affected by such hydrothermalism around Ghorabi and
viewers Dr. Walid S. Salama (CSIRO, Western Australia) and the
El Harra mine areas, where the vertical evolution of clay mineral as-
anonymous reviewer for their encouraging comments and annotations
semblages and transformation of smectite to illite/smectite mixed layer
that greatly improved an earlier version of the manuscript.

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Fig. 12. Sketch showing comparison between the two different models of ironstone formations: upper Cretaceous diagenetic ironstones and Eocene hydrothermal
ironstones, studied in the Bahariya Depression.

Appendix A. Supplementary data occurrences. Sediment. Geol. 329, 81–97.

Afify, A.M., Serra-Kiel, J., Sanz-Montero, M.E., Calvo, J.P., Sallam, E.S., 2016. Nummulite
biostratigraphy of the Eocene succession in the Bahariya Depression, Egypt:
Supplementary data associated with this article can be found, in the Implications for timing of iron mineralization. J. Afr. Earth Sci. 120, 44–55.
online version, at http://dx.doi.org/10.1016/j.oregeorev.2018.04.019. Baioumy, H.M., Ahmed, H.H., Mohamed, Z.K., 2014. A mixed hydrogeneous and hy-
drothermal origin of the Bahariya iron ores, Egypt: evidences from the trace and rare
earth elements geochemistry. J. Geochem. Expl. 146, 149–162.
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