Journal of African Earth Sciences, Vol. 26, No. 2, PP. 237-262.

1997
o 1997 Elssvier Science Ltd
Pergamon All rights reserved. Printed in Great Britain
Pll:SO899-5382(97)00101-2 . 0999-6382197 $17.00 + 0.00

Geochemistry of accessory minerals associated with

radioactive mineralisation in the central Eastern
Desert, Egypt

A. M. EL-KAMMAR,’ N. EL-HAZIK,2 M. MAHD12 and N. ALY2

‘Geology Department, Faculty of Science, United Arab Emirates University,
PO Box 17551, Al-Ain, UAE
2Nuclear Material Authority, Inshas, Cairo, Egypt

Abstract-Prominent shear zones in the low Ca granitic plutons of El-Missikat and

El-Erediya, central Eastern Desert of Egypt trend northwest-southeast, north-south
and northeast-southwest. The shear zones are filled with jasper containing uraniferous
mineralisation with accessory uranophane, pitchblende and uraninite, accompanied
by pyrite, galena, magnetite-titanomagnetite, ilmenite, hematite, rutile, titanite,
fluorite, zircon, monazite, apatite and tourmaline. It is possible to discriminate between
the mineralisation of the two prospects on the basis of the Pb and Cu content. The
El-Missikat veins contain more Pb and less Cu. compared to those of El-Erediya.
The mineralising hydrothermal fluid was ferruginous and highly enriched in many
trace elements but was markedly deficient in europium. The content of the high
field strength elements is mostly determined by the amount of zircon, monazite and
rutile. Colouration in fluorite is associated with considerable enrichment in the REEs.
Q 199 7 Elsevier Science Limited.

Resume-D’importantes zones de cisaillement dans les plutons B faibles teneurs en

Ca d’El-Missikat et d’El-Erediya, region centrale du Desert Oriental d’Egypte, sont
orientees NW-SE, N-S et NE-SW. Les zones de cisaillement sont remplies de jaspe
contenant des mineralisations uraniferes avec en mineraux accessoires de I’urophane,
du pitchblende et de I’uranite. accompagnees par de la pyrite, de la galene, de la
magnetite-titanomagnetite, de I’ilmenite, de I’hematite, du rutile, de la titanite, de la
fluorine, du zircon, de la monazite, de I’apatite et de la tourmaline. II est possible de
discriminer la mineralisation des deux gisements sur la base des teneurs en Pb et
Cu. Les filonnets d’El-Missikat contiennent davantage de Pb et moins de Cu, compres
B ceux d’El-Erediya.
Le fluide hydrothermal mineralisateur Btait ferrifere et tres enrichi in elements traces
mais il etait remarquablement deficient en Eu. La teneur en HFSE est determinee par
la teneur en zircon, monazite, et rutile. La couleur de la fluorine est Ii&e B
I’enrichissement en terres rares. e 1997 Elsevier Science Limited.

(Received 29 September 1995: revised version received 12 May 1997)

INTRODUCTION
Regional airborne radiometric and magnetic The mineralisation is strongly associated with
surveys have indicated the presence of several silicified shear and fracture zones that occur in
radioactive anomalies in the basement rocks of the peripheral parts of the two granitic plutons
the central part of ,the Eastern Desert of Egypt of El-Missikat and El-Erediya (El-Kassas, 1974;
(Ammar, 1973). Ground verification and Bakhit, 1978). The first pluton covers about 80
preliminary radioactive surveys led to the km* while the second covers about 70 km2 (Fig.
discovery of two anomalies at Gebel El-Missikat 1). Both plutons crop out in a fashion which
and Gebel El-Erediya. suggests that a larger mass has been divided by

Jo& of Af&m Earth Schmas 237

 A. M. EL-KAMMAR et al.

I Wadl Deposits

Cretaceous Nubla Sandstone

Post-Tectonic
Es3 Pink Granite
m Syn-Tectonic
Gray Granite

Metamorphosed
m
and Granltlzed
Ophlolitlc Rocks

Ophidltic Melange

- Faults and Shear Zone

ITUDY AREA
\
26” 20

Figure 1. Location and geological maps of the El-Missikat and El-Erediya occurrences.

a regional northwest left lateral strike-slip fault
(Assaf, 1994). There is a relationship between
the mineralisation and hydrothermal alteration
(Abu Dief, 1985; Mohamed, 1988).
Exploratory mining was carried out along the
shear zones. Due to the rugged topography of
the study areas and the fact that the mineralised
tracture zones dip against slope, galleries were
rendered prohibitive. A total of about 3829 m
of galleries were excavated in the study areas.
The present study focuses on the mineralogy
and crystal chemistry of the radioactive minerals,
of vein-type U deposits. The aim of the present
work is to understand more clearly the
significance of the major and trace element
distributions in the mineralised vein occurrences
of El-Missikat and El-Erediya, Eastern Desert,
Egypt.
GEOLOGICAL SETTING
The El-Missikat and El-Erediya areas are part of
the mountainous country in the central part of
the Eastern Desert of Egypt. They are mainly
composed of Precambrian igneous and
metamorphic basement, unconformably overlain
to the west by virtually undeformed flat-lying
sediments of the Nubia Sandstone facies (Fig.
1). The geology of the central Eastern Desert,
enclosing the two prospects, has been studied
by many authors, including El-Ramly (1972) and
Rabie and Ammar (1990). According to
Greenberg (19811, the two plutons were
emplaced during a post-tectonic episode in Egypt
(603-575 Ma).
The study areas are dissected by a network
of fractures of various trends of which the
northwest Najd Trend is the most pronounced.
According to Abu Dief (19921, both plutons are
characterised by the presence of more than one
tectonic phase, alternating with magmatic
activity and hydrothermal U mineralisation. The
oldest rock type exposed in the two areas is
represented by a tectonic melange followed by
metavolcanic rocks, then the older granitoids
and finally the younger granites or the late
collision pink granites. The latter are undeformed
leucogranites and are uniform in chemical and
 Geochemistry of accessory minerals associated with radioactive mineralisation

fi
0
.I

VI

In
._

e
VI

E
Q

t:

Wave Number cm-’

Figure 2. tnfrared spectrograms of la) uranophane separated from El-Missikat and 1bl pitchblende
from El-Erediya.

mineral composition within an individual pluton METHODOLOGY

(Hashad, 1980). On the basis of mineralogical Sampling
and radiometric studies, Hussein and Sayyah Since the mineralisation is mainly confined to
(19921 concluded that the U occurrences of El- the jasper filling the fractures in the shear zones,
Missikat and El-Erediya are of vein-type where samples were mainly collected from the U
the mineralising fluids have their source in the mineralisation and its direct host rock (i.e. black
granitic magma itself. silica and jasper). Twenty samples were
On the basis of the cross-cutting relationships collected from underground mining works, 16
observed in the exploratory mining work, the from the jasper veins and four from the pink
siliceous material that occupies the shear zones granites. Samples were collected so that the
in the El-Missikat area can be classified into three different grades of mineralisation were
generations: represented.
il light coloured;
ii) smoky to black; and Sample analysis
iii) jasper. The mineral analysis was done by X-ray
Alteration processes, including silicification, diffraction (XRD, CU-Ka radiation), differential
kaolinitisation, sericitisation and hematisation, thermal analysis (DTA) and infrared spectrometry
are common along the structural lines and around (IR) methods.
the shear zones (Abu Dief, 1985). Uranophane Chemical analysis of whole samples was
was identified by Bakhit (19781, Ahmed (1991) performed by corroborative wet and conventional
and others as fracture-filling and as methods, including:
disseminations in the black silica and jasper. In ij flame photometry for Na and K;
the El-Erediya area, the mineralised zones are ii) inductively coupled plasma (ICP) technique
controlled by north-south to northeast-southwest for Ba, Cu, Ni, Rb, SC and Y;
and northwest-southeast fractures with infilling iiil X-ray fluorescence (MO target) for Nb, Pb,
jasper veins hosting U minerals such as Sr, Zn and i!r; and
pitchblende, uranophane and renardite (El- vi) instrumental neutron activation analysis
Kassas, 1974; later confirmed by Assaf, 1994). (INAA) for the analysis of the REEs, using thermal

Journal of Afrfcan Earth .Vdences 239

 A. M. EL-KAMMAR et al.

neutron flux (1012 cm.* s-l) of a 2 MW research modification peak of quartz at 573OC, as well
reactor. as the uranophane dehydration endothermic
A series of standards, including G-2, GSP-1 peaks at 103OC, 207OC and 371 OC and the
and BCR-1, in addition to some synthetic recrystallisation exothermic peak at 736OC.
standards, were adopted as reference materials. Moreover, the IR spectrogram produces
The fluorimetric technique (N laser) was used absorption bands at 1080, 1030 and 1005 cm.’
for the analysis of U, while the colour due to SiO, stretching, in addition to the
spectrophotometry technique was used for the asymmetric and symmetric stretching bands of
analysis of Th after being extracted by ion- the uranyl group at 1000 and 900 cm-’ (Fig.
exchange resin. 2a). The stretching of OH and the deformation
An electron microprobe (model JXA-8600) was of the HOH groups in uranophane produce strong
used for the analysis of the individual minerals absorption bands at 3420 and 1630 cm-‘,
separated from the mineralised occurrences, at respectively.
an accelerating voltage of 15 kV and specimen Uraninite is detected for the first time in the
current of 5-l 0 mA (measured on brass). Well silica veins of the El-Missikat occurrence as
characterised natural minerals and artificial glass opaque grains displaying a grey colour with
were used as standards. brownish tints (markedly lower reflectance than
magnetite), under reflected light. The sharpness
of its main X-ray diffraction peaks (3.14/100,
HEAVY MINERAL IDENTIFICATION 2.73/50, 1.93/80 and 1.65&80) is improved
The heavy minerals identified in the occurrences after being heated to 9OOOC.
studied can be classified into: (1) U minerals; Pitchblende was recorded only in the El-
(2) sulphide minerals; (3) Fe-Ti oxides; and (4) Erediya occurrence as grains having optical
miscellaneous transparent minerals. properties, under reflected light, closely similar
to those of uraninite. The sharpness, as well as
Uranium minerals the relative intensity of the main d-spacings of
Uranophane is identified as a prominent the pitchblende diffractogram, markedly
secondary mineral in the mineralised silica veins improves upon heating to 900°C (Table 1 I. The
of both occurrences. It tends to concentrate in DTA diagram shows diagnostic exothermic
the 1.5 A non-magnetic fraction. It is massive peaks at 330°C and 730°C, which can be
and displays different shades of yellow. Its XRD attributed to oxidation of UO, to U,O,
pattern is very similar to the standard ASTM (Mackenzie, 19701, while its endothermic
data (card No. 8-442). The presence of very dehydration peak appears at 17OOC. The
finely disseminated quartz impurities within the infrared stretching bands of the uranyl group in
uranophane could not be detected by XRD due pitchblende appears at 1080, 1000 and 900
to the interference of the main d-spacings. cm-’ while those of OH groups appear at 3420
However, the DTA diagram shows a clear and 1645 cm“ (Fig. 2b).

Table 1. X-ray diffraction data of heated and unheated pitchblende separated from the
El-Erediya mineralisation

240 Journal of African Earth Sciences

 Geochemistry of accessory minerals associated with radioactive minerafisation
Sulphide minerals
The ore microscopic examination, aided by XRD
analysis, indicates that galena and pyrite are the
only detectable sulphide minerals. Pyrite is always
affected by a slight alteration into goethite.
Concentrates of almost pure galena and pyrite
were obtained by magnetic separation at 1.5 A
non-magnetic and 1 .O A magnetic fractions,
respectively, followed by intensive purification
by hand picking under a binocular microscope.
Iron-titanium oxide minerals
The identified minerals of this group are
magnetite, ilmenite,, hematite, rutile and titanite,
in decreasing order of relative abundance.
Magnetite, or rather titanomagnetite, appears
as subhedral crystals under reflected light, with
an increasing pinkish tint with an increase in its
Ti content. It is martitised to hematite,
particularly at the crystal margins. Martitisation
occurs as wide lamellae, which can be
interpreted as due to atmospheric oxidation
(Ramdohr, 1980).
llmenite is mostly concentrated within the 0.2
A magnetic fraction. It appears under reflected
light as euhedral to subhedral crystals. It shows
various aspects of exsolution intergrowths, such
as hematite-ilmenite, which originates
temperatures above 600°C (Basta, 19531,
ilmenite-rutile-hematite, probably due to poor
mixing, and rutile-anatase. Moreover, ilmenite
seems to have been subjected to further
alteration and replacement by sphene. Hematite
may occur as discrete grains with a moderate
reflectivity and weak bireflection, especially
when using oil immersion. Rutile occurs as both
transparent and opaque varieties, with a
predominance of the former as reddish prismatic
crystals. The opaque variety shows well-
developed twinning of yellowish to orange
internal reflection.
Miscellaneous transparent minerals
Fluorite is the most common transparent
accessory mineral in the mineralised silica veins,
particularly those of the El-Erediya occurrence.
Fluorite displays considerable variation in colour
from colourless to deep purple. Such changes
in colour are attributed to emanations from (or
inclusions of) nearby radioactive material, traces
of REEs or others (Deer et al., 1992) or to the
presence of Y in particular (Fayziev, 1990). Upon
treatment with DTA, fluorite displays a change
in colour from colourless to purple while
producing a series of exothermic reaction peaks
at 310, 350, 520 and 96OOC.
Two varieties of zircon are distinguished:
i) a colourless and transparent non-magnetic
variety; and
L+IIa coloured magnetic variety with preferential
growth of the pyramidal faces at the expense
of the prismatic ones.
Although some authors such as Pupin and
Turcon (1975) attributed the development of the
bipyramidal variety to many factors, such as slow
crystallisation, agpaicity of the magma and
substitution by U, Th, REEs and P, Speer (I 982)
concluded that it is difficult to relate the
morphology to any one condition.
The IR spectrogram of zircon is made up of
both internal and external modes of vibration.
According to Woodhead eta/. (I 9911, the former
involves bending and stretching of the Si-0
bonds in discrete silica tetrahedra, while the
external mode involves translation and rotation
of nearly rigid tetrahedra in relation to Zr cations.
The vibration bands at 970, 899, 439, 383 and
319 cm-’ are generally weakened and broadened
in the analysed zircon. Deliens et al. (I 977) and
Woodhead et al. (op. cit.), explained that
metamictisation of natural zircon due to crystal
damage was caused by radiation decay from
trace amounts of U and Th substituting for Zr.
at Other transparent minerals, such as apatite,
tourmaline and monazite, are distinguished as
non-significant accessories.
RELATIVE ABUNDANCE OF ELEMENTS
The chemical analysis data of the mineralised
silica veins and their host granites (Table 21
suggest the following inferences:
i) The younger granitic plutons of El-Missikat
and El-Erediya are generally low in Ca and the
latter area is more sodic than potassic. According
to Meyer et al. (19941, such low Ca, S type
granites contain distinctive accessory minerals,
comprising zircon, apatite, zircon bearing
silicates, Ca-Th phosphates, very rare xenotime
and early monazite, and have a chemical
signature consistent with derivation from a
metasedimentary precursor. Their average
normative composition is: quartz 35.1%; alkali
feldspars 60.9%; anorthite 2.7%. The granites,
especially those of the El-Erediya occurrence,
are relatively enriched in a sizable group of trace
elements, including Co, Nb, Ni, Rb, Y and U, but
depleted in others, such as Ba, Pb, Sr, Zn and Zr.
iii Silica veins are enriched in Fe,O, by a factor
of three, compared to their host granites. The
veins of both occurrences are also markedly
enriched in all the analysed trace elements,
Journal of African Earth Scbnces 241
Table 2. Chemical analysis data of major and trace elements of the studied mineralised silica veins and thei< host granites.

lOxide&mples NumberI MineraliiedSilica Veins of El-MissikatOccurrence {Average 1 Sample Number I MineralizedSiticaVeins of El-ErediyaOccurrence
twt.%t;12)314t5t617(81 Granite’
- I 9 .hOIll 12 13 1 14 15 16 1Granite’
85.90 88.001 88.40 87.80 87.00174.98
0.011 0.011 0.02 0.011 0.021 0.10

P205 1 0.25 0.10 0.19 0.15 0.01 0.03 0.03 0.03 N.A. 0.09 0.01 0.01
L-0.1.1 2.07 2.40 1.50 1.70 2.60 1.50 2.01 3.01 N.A. 1.60 1.90 2.40
-.
SC . I Ql 61 “[ ‘1 31 JI ';I 1r.n.t
Cd 2; 3; 3;; 2; 2; 3; 3; 2; 2; 3; 34 32
Ni 22 60 49 12 11 56 56 31 13 64 66 63
32 36
172 410 109 172 342
181 25 136 21 129
207 168 99 169 72
163 55 99 80 87
164 214 92 226 143
# 45 360
--- 4E 46 31
2571' 1881 l& I 291 196
2070 1571 1031 789 15 156 172
[[I 31 29 31 29 15 15 13
800 1220 820 770 15 200 489
*Averagesof ISMissikat&
El-Erediya
granites
by Greenberg (1981)
N.A.**means notanalyzed.
 Geochemistry of accessory minerals associated with radioactive mineralisation

??
ZOOO-

El-Missikat
Silica Veins
??
1500 -
ii II
n II

If 1000 - ??

?? El-Erediya
Silica Veins
??
500- L

0
?? cl L
0

10 15 20 25 30 35 40

Cw fwm

Figure 3. Relation.ship between Cu and Pb in the two studied prospects.

except for Rb which seems to be controlled by LREE:HREE ratios, while those of El-Missikat are
the K bearing minerals of granites. preferentially enriched in the HREEs by at least
iiil High field strength elements (HFSE), such two orders of magnitude (Fig. 4). Such REE
as Zr, Th and Nb, reflect the character of patterns reflect the more uraniferous nature of
accessory minerals. For example, Zr, Hf and the El-Missikat occurrence, where uranophane,
some Th occur in zircon, while monazite hosts uraninite, pitchblende and monazite are all
the majority of Th and Nb is mainly within the Ti identified by their higher selectivity for LREEs
sites of rutile, which contain between 100 and over HREEs. However, Flynn and Burnham
1000 ppm Nb. The notable enrichment in most (19781, Humphris (1986) and Wood (1990)
HFSEs can be attributed to their partitioning into demonstrated empirically and experimentally the
an F rich vapour phase that has most probably importance of Cl- F- and CO,*- in transporting
been separated from a highly fractionated REEs as complexes in high salinity solutions and
granitic magma (Woodhead et al., 1991). at temperatures probably not below 2OOOC. The
However, Meyer et a/. (19941, believe that these presence of fluorite in both occurrences may
HFSEs are not amenable to modelling in terms suggest F-complexing for REE from the
of crystal-melt equilibria. hydrothermal fluids, in addition to the accessory
iv) The El-Missikat occurrence shows a minerals acting as REE accumulators.
dominance of Pb over Cu (Fig. 31, perhaps vi. There is no noticeable Ce anomaly, but an
because of the relative abundance of galena over almost consistent strong negative Eu anomaly
chalcopyrite, compared to the El-Erediya (-0.4 to -0.6) exists in the mineralised veins and
occurrence. their host granites in both occurrences. This REE
v) REE patterns can be used to distinguish behaviour is most probably inherited from the
between rock types (Asubiejo and Ige, 1992). parent granitic magma.
Monazite is enriched in light REEs, zircon in vii) A relatively strong negative Yb anomaly
heavy REEs and apatite in middle REEs (-0.4 to -0.57) can be distinguished for the
(Henderson, 1984). The mineralised veins of El- mineralised veins, but not for their host
Missikat are enriched in CREEs by a factor of granites. Since Yb3+ is less mobile under
36, while those of El-Erediya are enriched only oxidising conditions (Henderson, 19841, it
by a factor of 7, compared to their host younger could be inferred that the mineralised veins
granites. The mineralised veins of El-Erediya and were most probably formed under oxidising
their host granites display rather similar conditions.
 A. M. EL-KAMMAR et al.

+ El-Missikat silica veins

* El-Erediya silica veins
--o-- El-Miss&at granite
__.O_..._ El-Erediya granite

+ Taylor andMcLennan (1985)

b
l- I ‘ I8 I * I I I I I I1

La ce Sm ELI Gd Tb Yb Lu

REE, Atomic Number

Figure 4. Chondrite normalised REEpattems of both the mineralised veins and their host granites
in the El-Missikat and El-Erediya occurrences.

CRYSTAL CHEMISTRY
The separated minerals, being of small mass,
were analysed by electron microprobe and
instrumental neutron activation analysis (INAAI.
The data on the crystal chemistry of the
individual minerals contributes significantly to
the available knowledge on the genetic controls
of the mineralisation in both the El-Missikat and
El-Erediya occurrences.
Uraninite
The average chemical composition of uraninite
suggests the following formula:
Four electron microprobe analyses along an
intercept of a uraninite grain (Table 31 indicate
an absence of zoning. The relatively high REE
budget in uraninite may suggest, according to
Fryer and Taylor (I 9871, high-temperature
mineralisation associated with granitic rocks. The
content of Pb, which is believed to be mostly of
radiogenic origin, increases from 8.99% at the
centre of the grains to 9.30% at the periphery.
The minor concentrations of Si, Fe and Ti in
uraninite cannot be attributed to atomic
 Geochemistry of accessory minerals associated with radioactive mineralisa tion

Table 3. Electron microprobe analysis data of uraninite from the

mineralised veins of El-Missikat

Table 4. Electron microprobe analysis data of pitchblende

from the mineralised veins of El-Erediya

La, Ce, Sm, Eu, Tb, Yb and Lu are determined by INAA

technique to be 375,429, 23,1.56, 1.7.0.45 and 0.097
ppm, respectively.

substitution, but more likely to finely disseminated
inclusions.
Pitchblende
Abu Dief (1992) estimated an age of 160 Ma
for the pitchblende of El-Erediya using a U/Pb
method. Three electron microprobe analyses in
a pitchblende grain (Table 4) suggest the
following average formula:
(U,.,,Ca,.,,Pb,,,REE,.,,)C*
The REE pattern of pitchblende, as estimated by
INAA, indicates a remarkable enrichment of XREEs
(830 ppm) with strong LREEs enrichment relative
to HREEs, and a sharp negative Eu anomaly of -
0.62 (Figs 5 and 6). During the formation of
pitchblende, the REEs are leached from the altered
granites and may be incorporated into the lattice
of newly formed minerals. On the basis of the
relative stability of HREEs, the carbonate
complexes remain partly in solution, whereas the
LREEs tend to be concentrated in the pitchblende
lattice. The similarity in the ionic radius of the
LREEs3+ (1.13-1.04 A) and both U4+ and Ca*+
may suggest a possible accommodation of LREEs
in the pitchblende lattice, via a coupled atomic
substitution mechanism. The relatively high
contents of SiO, ( > 5Oh) and Fe,O, (~2%) are most
probably due to inclusions.

Joumd of Afrkm Euth Sckmces 246

 A. M. EL-KAMMAR et al.

56 57 56 62 63 65 66 70 71 72

R E E s, Atomic Number
--t Pitchblende +Colouriess Fluorite -E-Viola; Fluorite -X-Zircon 1

Figure 5. Chondrite normalised REE patterns of individual accessory minerals separated from the studied mineralisations.

Table 5. Electron microprobe analysis data of uranophane from the

mineralised veins of El-Missikat

U308 1 66.59 66.371 66.201 66.65 66.45

1-120(+I 1 11.42 11.661 12.671 12.56 12.09
b.l. Means below detection.
La, Ce, Sm, Eu, Tb, Yb and Lu are determined by INCA technique
to be 142.187, il. 1.5, 0.8, 0.28, 0.03 ppm, respectively.

Uranophane Sulphide minerals

This monoclinic uranyl silicate is fairly common Trace elements in sulphides may be present
in the oxide zone of most U deposits (Cesbron as admixed solid inclusions fluid inclusions,
er a/., 1993) and its U to Si ratio is about 1: 1. various types of substitution, interstitial or
The average composition of the analysed “proxy” solid solution or to finely intergrown
uranophane (Table 5) can be expressed in the exsolution products (Table 6). In galena, the
following formula: main substituents for Pb are Sb (0.18-0.3956)
and Ag (0.20-0.35%). Galena owes its minor
concentrations of Zn and Cu to tiny inclusions
of sphalerite and chalcopyrite. The absolute
As with pitchblende, uranophane displays a concentration of Ag, as well as the Ag/Sb
strong enrichment in LREEs and a marked ratio, coincides perfectly with the published
deficiency in Eu (Figs 5 and 6). The REEs occupy data on galena of hydrothermal origin (Hall
the Ca sites in the lattice. and Czamanske, 19721, rather than those of

246 Journ.?l of Aft&an Earth Sciences

 Geochemistry of eccessory minerals associated with radioactive mineralisa tion

AEu

Figure 6. Europium anomaly in the mineraked silica veins and the individualaccessory minerals.

Table 6. Electron microprobe analysis data of galena from the mineralised veins of El-Missikat

-~
b-1. means below detection.

Journal of African Earth Sciences 247

 A. M. El-KAMMAR et al.

Table 7. Electron microprobe analysis data of pyrite from

the mineralised veins of El-Missikat

b.1. Means below detection.

Table 8. Electron microprobe analysis data of monazite from the

mineralised veins of El-Missikat

metamorphic, sedimentary or supergene The data suggest a rather homogeneous

origin.
The analysis of three pyrite grains (Table 7)
indicates that Co and Ni are the main
substituents for Fe*+. The content of these two
trace elements and their ratio (Co/Nil, is also
very similar to the data published on
hydrothermal pyrite.
Monazite
Monazite, which is the most common REE bearing
mineral, has a preferential selectivity towards the
LREEs and is also known as an ultrastable mineral
during weathering. Its chemical formula has been
calculated on the basis of an average of four
electron microprobe analyses (Table 8):
composition, except for Y3+ (0.92 A) and Dy3+
(0.92 AI. In agreement with Jefferies (19851,
the substitution of CaZ+ by REEs3+ seems to be
controlled by the entry of Th4+ in the monazite
lattice; Ca2+ + Th4+02REEs3+.
Uranium (0.20-0.26% U,O,) may also occupy
some of the REE sites in monazite (Hughes et
al., 1991 I. The CREE content is estimated to
be 63.31%, 99.56% of which belong to the
LREEs. The CREE content seems to be less than
the empirical requirement of the monazite lattice
(69.72%3, most probably due to substitution
by Ca2+ Th4+ and U4+. The excessive enrichment
of LREEs over HREEs in the analysed monazite
is accompanied by a sharp Eu deficiency (Eu,=
-1.081, which is most probably a result of an
earlier preferential accumulation of EuZ+ in

248 Journal of African Earth Sciences

 Geochemistry of accessory minerals associated with radioactive mineralisation
Table 9. Electron microprobe
mineralised veins of El-Missikat
b.1. Means below detection.
La, Ce, Sm. Eu, Tb and Lu are dtetrmined by INAA techniaue
to be 8, 45, 50.6, 120 and 44 ppm. respectively.
plagioclase under reducing conditions (Figs 5
and 6).
Zircon
The chemistry of zircon is relatively simple,
where ZrO, and SiO, usually comprise more than
95%, with possible substitution by Y, REEs, Hf.
Th and U. The substitution may take place either
in the tetragonal sites of Si or the triangular
dodecahedral sites of Zr (Speer, 1982). The
average chemical formula, as calculated from
four electron microprobe analyses (Table 91, can
be expressed as follows:
Microscopic examination indicates that most
zircons display both optical and compositional
zoning. Probe analyses show that substitution
of Zr by Hf, U, Th and REEs increases at the
grain periphery, which corresponds to the latest
stage of zircon crystallisation. The radioactivity
of the analysed zircon is related to U rather than
to Th, where the U content (0.23%) is about
eight times that of Th, indicating that the zircon
crystallised in a comparatively highly uraniferous
medium.
The atomic substitution of REEs for Zr in zircon
can be explained in terms of ionic radius (Heaman
et a/., 1990). The content of CREEs + Y is
estimated to be 0.18%, 98.5% of which is
accounted for by Y, Yb and Lu. Such sharp HREE
selectivity by zircon is accompanied by a very
strong Eu-deficiency (Eu,= -1.1 1; Figs 5 and 6).
As with monazite, the Eu deficiency in zircon
can also be interpreted as an accumulation of
analysis data of zircon from the
Eu by earlier plagioclase or other Ca bearing
minerals under reducing conditions.
Fluorite
The analytical data of colourless and violet
fluorite grains (Table IO) suggest that the violet
variety contains more than twice the REE content
of the colourless variety (768 and’309 ppm,
respectively). More than 70% of the REE content
belongs to the Y group (i.e. HREEs). According
to Bulnayev and Kaperskaya (I 9901, the factors
governing the distribution and concentration of
trace elements include the temperature and
relationship of the mineralisation to a particular
type of magmatic rock. The elevated alkalinity
in the melts and the mineralising solutions also
play an important role, where the presence of F
may cause full separation of REEs and hence
preferential accumulation of the HREEs as
fluoride. Luders et a/. (I 993) and Bau and Dulski
(I 995) believe that a positive Eu anomaly is a
diagnostic feature of fluorites and carbonate
minerals that crystallise from aqueous liquids
under slight reducing conditions at temperatures
above 250°C. The data on the fluorites studied
indicate an unusual REE pattern (Figs 5 and 6)
displaying a strong Eu depletion (Eu,=-1.75) and
therefore the Eu deficiency is unrelated to the
colouration or REE budget of the fluorites. It
would therefore appear that the assumption of
Luders et a/. (1993) is overstated, or at least
not applicable to every hydrothermal fluorite. It
seems more logical to believe that the Eu
anomaly, whether positive or negative, is related
to the composition and differentiation regime of
the hydrothermal solution rather than to its
 A. M. EL-KAMMAR et al.

Table 10. (a) Neutron activation analysis of colorless and

violet fluorites, and (b1 Microprobe analysis data of banded
fluorite from El-Erediya occurrence.
1

Colorless Fluorite Violet Fluorite

Ch.Norm* ppm Ch.Norm’
19.00 56.00 49.00 144.00
54.00 59.00 140.00
-. n ;,.7.00
._ _, 87.00 36.00
_. 1sl
n ._ 2~001 0.4
_.12
38.00 146.00
---- 89.00 342.00
149.00 677.00 375.00 1705.00
;JZ.UUl v41 .UUl rv.uul 2324.00
I I I
Total REE 309.00 768.00
Ce/Yb (N) 0.09 0.09
EU anamaiy -1.75 -1.60
?? Chondritenamalii values

Elements Individual banded crystal

Wt.% a* b” 1 c’ I
Ca 50.25 SO.781 49.90 -50.10
Y 0.08 0.091 0.06 0.15
Na 0 02 0.031 0.01 0.06
D2

Note: There are trace of U, Si, Fe and Al in the violet bands.

temperature or redox potential. In the study a coupled atomic substitution mechanism as

occurrences, the hydrothermal solutions must follows:
have been excessively depleted in Eu, since all
the analysed accessory minerals reflect a certain Y3+ (REEs3+) + Na+ e 2 Ca*+ (W+)
degree of Eu deficiency (Fig. 6). However, the
Eu deficiency cannot simply be explained in terms
of Gibbs free energy (i.e. stability), which regards CONCLUSIONS
EuF, and YbF, as the least stable among all the Potential U mineralisation is associated with
REEF,, while there is no anomaly of Yb in the fractures and shear zones of two granite plutons
studied fluorite. The melt, from which the in El-Missikat and El-Erediya in the central part
mineralising hydrothermal solutions were of the Eastern Desert of Egypt. The most
segregated, had experienced strong reducing dominant fractures trend northwest-southeast
conditions that may have caused an excessive (Najd Trend). Mineralisation is confined to
concentration of Eu*+ in early formed Ca minerals. secondary in filling of shear zones by three
The change in colour of fluorite from colourless varieties of silica; jasper, light coloured silica
to violet seems to be controlled by the Y content and smoky to black silica, with the first being
in particular, and the Y group in general. The Y the most mineralised. The minerals identified
content increases from about 0.06% in the are classified into four groups: U bearing,
colourless variety, to about 0.15% in the violet sulphides, oxides and miscellaneous transparent
variety. The increase in the content of Y is minerals. The U bearing minerals include
accompanied by an equivalent increase in the uranophane, pitchblende and uraninite. The
content of Na, and decreases in both Ca and Sr latter was identified for the first time in the
(see Table 10). These abundance relationships El-Missikat occurrence during this study.
may be explained by Y and REEs occupying the Pyrite, chalcopyrite and galena were the only
8-fold co-ordination sites of Ca in fluorite through sulphides detected, while oxides are quite

250 Journal of African Earth Sciences

 Geochemistry of accessory minerals associated with radioactive mineralisation

variable, with magnetite-titanomagnetite, Asubiojo, 0. J. and lge. 0. A. 1992. Rare earth element
patterns in ultramafic rocks of the schist belt of South
ilmenite, hematite, rutile and sphene were
Western Nigeria by instrumental neutron activation
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abundance, are fluorite, zircon, monazite, Articles 158, 193-200.
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Ain Shams University, Cairo, Egypt.
i) The granitic plutons are of the Ca low type. Basta, E. Z. 1953. Mineralogical aspects of the system FeO-
Their average normative composition is 35.1% Fe,O,-TiO,. Ph. D. Thesis, Bristol University, UK.
quartz, 60.9% alkali feldspars and 2.7% Bau, M. and Dulski, P. 1995. Comparative study of yttrium
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deposits in Transbaykalia. Translated from Geokhemiya
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the main accumulators of HFSEs in the mineralogical data on uranophane and j3-uranophane:
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Deer, W. A., Howie, R. A. and Zussman, J. 1992. An
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Flynn, R. T. and Burnham, C. W. 1978. An experimental
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252 Journal of African Earth Sch?nces