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***
Faculty of science, El Fayoum University, Egypt
The study of chemical zoning, color and pleochroism of cassiterites aids in understanding of the metallogeny
and exploration of the primary Sn source. These characteristics assist in discriminating the host granitoids into
two associations: metasomatized granites and lithium albite granites.
The cassiterite of the metasomatized alkali feldspar granites (i.e., apogranites) is characterized by enhanced
to moderate Nb, Ta, (with high Nb/Ta ratios), Ti, FeO* and lower Ga2O3 (<0.01 wt%). Also, it is characterized
by the development of deep brown to dark brown pleochroic color zones which oscillate or progressively alter-
nate with lighter color zones. On the other hand, the cassiterite in the lithium albite granite is enriched in Ta, Nb
(with low Nb/Ta ratio), Ti, FeO*, and Ga2O3 0.01 0.04%. It is also characterized by deep orange to reddish
- -
brown pleochroic core or bands which are alternate with lighter color bands.
It is noteworthy that the conspicuous variation in the colors, pleochroism, and chemistry of cassiterite from
metasomatized apogranites and lithium albite granites can be considered as a valuable exploration tool when
prospecting for primary cassiterite mineralization. In other words, during the panning survey, which is largely
applied to rare metal mineralizations in general and cassiterite deposits in particular (where cassiterite is essen-
tially dispersed in the mechanical aureoles), the pleochroism of any cassiterite present indicates the nature of
the primary mineralizations (i.e., magmatic or metasomatic).
INTRODUCTION rin et al., 1971; Sabet et al., 1976a, 1976b). These geolo-
gists have attributed the formation of rare metal mineral-
Stanniferous or tin bearing granitoids are those genetical-
-
ization to the metasomatic alteration processes affecting
ly and spatially associated with cassiterite mineralization. the host granites. In the Pan African shield that is mainly
-
rocks. They are both petrographically and geochemically the present study) can be classified into two types of asso-
specialized, particularly their anomalous concentrations ciations; i) metasomatized granite and ii) lithium albite
of elements such as F, Li, B, Sn, and Rb (Tischendorf, granite.
1977). Formation of rare metal granitoids in general and
-
In the first case, Sn mineralization is associated with
stanniferous ones in particular can be attributed to mag- the alkali feldspar granites which that have suffered post -
1992; Abdalla et al., 1998; Abdalla and Mohamed, 1999). granites in the sense of Beus et al., 1962; Abdalla, 1996;
One of the most important discoveries in 1970 was Abdalla et al., 1998). Meanwhile, cassiterite belong to the
the detection of rare metal mineralization in apogranites second types of association is related to lithium albite -
of the albitite type in the Central Eastern Desert of Egypt granites which are formed as ultimate differentiates from
by a group of Soviet and Egyptian geologists (e.g., Babu- haplogranitic melt by simultaneous crystallization of min-
doi:10.2465/jmps.070528a erals from melt and fluid under conditions of high aF, Li ;
H.M. Abdalla, dr_hma_enma@yahoo.com Corresponding author the activities of lithium and fluorine; (Pollard, 1983;
Chemistry of cassiterite in rare metal granitoids and the associated rocks 319
Figure 1. (A) Location and detailed geological maps for some of the investigated Cassiterite-bearing granitoids, Eastern Desert, Egypt. (B)
Geological Map of Abu Dabbab lithium-albite granite (modified from Sabet et al., 1976b). (C) Geological map of Mueilha apogranite (modi-
fied from Soliman, 1984).
Kovalenko and Kovalenko, 1984; Schwartz, 1992). (i.e., chemical, morphological, color and pleochroic char-
The present study is concerned with the cassiterite acteristics that typically develop under specific physico-
mineral chemistry of the aforementioned lithium albite chemical conditions). Four tin bearing stocks were se-
-
granite and metasomatised granitoid associations. This lected to achieve the goals of the present study. They are:
study seeks to clarify the physico chemical conditions re-
- Homr Akarem and Mueilha for metasomatized granitoids
sponsible for the evolution of these granitoids through de- and Igla and Abu Dabbab for lithium albite granite asso-
ducing the typomorphic characteristics of their cassiterite ciation (Fig. 1).
320 H.M. Abdalla, H. Matsueda, M.A. Obeid and R. Takahashi
Table 1. Selected EPMA analysis of the investigated cassiterite of stanniferous granitoids, Egypt
*
Analysis Nos. 1, 2, 5, 8 and 10 refer to light-colored zones; 3, yellowish-orange (intermediate colored) zone; 4, 6, 7, 9 and 11 refer to dark-
colored zones in the investigated cassiterite.
**
Total iron as FeO.
- , below detection limit.
The metasomatic nature of the investigated metaso- Hokkaido University, Japan) has been used for analyzing
matized granitoids and the magmatic characters of the polished thin sections and polished thin grain mounts ob-
lithium albite granite stocks were based on the criteria cit- tained from placer samples (Fig. 2). Standards used for
ed by Pollard (1983), Schwartz (1992), Abdalla (1996), EPMA analysis were synthesized pure oxides and natural
Abdalla et al. (1996) and Abdalla et al. (1998). Detailed minerals. The operating conditions were an accelerating
geochemical characteristics of the investigated tin bearing- voltage of 15 kV, probe current of 5 nA, a beam diameter
granitoids can be found elsewhere (e.g., Abdalla et al., of about 1 μm and counting time of 20 seconds. The ob-
2008; Abdalla, 2008). tained total weight percents were fairly reasonable within
the acceptable range of 100% ± 2.5%. Some analyses
SAMPLING AND ANALYTICAL TECHNIQUES were selected (Table 1) to show the variations among the
composition of the investigated cassiterite.
An electron probe microanalyzer (JEOL JXA 50A in -
Figure 2. Textural characteristics of cassiterite in stanniferous granitoids, Eastern Desert of Egypt. (A) and (B) Photomicrographs showing dis-
seminated cassiterite crystal which is included within lithium muscovite in Abu Dabbab Li-albite granite. Notice that the cassiterite crystal
is zoned with deep-brown core and pale yellow rim. (C) Polished slab showing cassiterite-bearing exo-greisen vein cutting across the coun-
try metasediments, Mueilha apogranite. (D) Polished slab showing cassiterite veinlet cutting through Igla lithium-albite granite. Notice that
cassiterite constitutes more than 95% of the veinlet. (E) Rolled pebbles of placer cassiterite, stream tin, Igla tin field. Notice that some nug-
gets exhibit the characteristic elbow-shaped twins. (F) Thin polished grain mount for the Igla placer cassiterite. Notice the development of
color zoning (with different styles, refer to the text) which grades from colorless to nearly opaque. (G) Oscillatory zoning in Igla cassiterite.
(H) Cssiterite crystal exhibiting the elbow-shaped twinning and the characteristic reddish-brown color and pleochroism, Igla cassiterite. (I)
Rolled and twinned cassiterite pebble that exhibit crystallographic boundaries consisting of many close planes indicating repeated twinning.
The planar growth color zones parallel to natural face are seen to have been contoured with some zones become discontinuous at the twin-
ning planes. (J) Wood tin with the characteristic colloform texture. Notice the development of hematite inclusions. Abbreviations: Ct, cas-
siterite; Lm, lithium muscovite; Ms, muscovite; Q, quartz; Ab, albite; Met, metasediment country rock; Gr, granite; Ec, Elbow-shaped twin;
Dis, discontinuous color zoning; Cl, colloform-textured cassiterite; He, Hematite inclusions.
Chemistry of cassiterite in rare metal granitoids and the associated rocks 321
On the basis of field and petrographical studies, the inves- These granites occur as small stocks, 0.2 to 4 km2 in area,
tigated tin bearing granitoids are classified into two types
-
with circular to dike like outcrops. They are characterized
-
grained and randomly oriented albite, K feldspar, Li- bitized granite (zone of Na metasomatism). Moreover, a
-
mica, topaz and quartz. The accessory minerals include smaller volume of greisenized (H+ metasomatized) or
-
The stocks commonly display a petrographical zonal covered) of the investigated apogranites. Textural charac-
pattern in response to their magmatic evolution as exem- teristics are dominantly of subsolidus metasomatic replace
plified by the Abu Dabbab granite, with lower medium - ments.
grained albite granite and a roof zone of fine grained, - The mineral constituents of the deeper unaltered al-
lithium white mica albite granite (Fig. 1B). Moreover, the
- kali feldspar granite zone are microcline and microcline
roof zone is capped by a carapace of banded pegmatoidal, perthite, plagioclase (An3–8), quartz and white mica with
stockscheider, crust (0.5 to 4.5 m thick) with an upper traces of siderophyllite mica. Texturally, white mica oc-
band consisting of gigantic quartz crystals and a lower curs as subhedral interstitial, fine to medium sized flakes
- -
The quartz crystals commonly grow inward from the The accessory minerals are zircon, fluorite, ilmenite, py-
granite/country rock contact and show no evidence for rite, cassiterite and rare columbite.
late emplacement of the pegmatite crust. Furthermore, a In addition to the development of Li siderophyllite
-
matic processes, with a deeper unaltered zone of alkali 2G 2I). For simplicity the colored zones are classified
-
feldspar granites capped by bleached gray to whitish, al- into three shades namely: i) light (i.e., colorless, white,
Chemistry of cassiterite in rare metal granitoids and the associated rocks 323
and lighter zones alternate rhythmically and may form tioned before, this cassiterite is characterized by the de-
more than 30 oscillations within a single crystal. Oscilla- velopment of a deep orange to reddish brown pleochroic
-
tory zoning was clearly visible from the core to rims and core or bands that are rimmed or oscillatory alternated by
hence it can be considered a type of concentric zoning. lighter bands. The dark zones are conspicuously enriched
However, in some crystals, oscillatory zoning seemed to in Ta, Nb, Ti, Fe and Ga relative to the lighter ones (Table
be specific to distinct concentric growth crystallographic 1, and Figs. 3 5).
-
direction. In such cases, weak oscillatory zoning appeared On the other hand, cassiterite of the metasomatized
when the resolution of the BSE (back scattered electron)
- apogranites (e.g., Mueilha and Homr Akarem) is charac-
image was enhanced. terized by enhanced to moderate Nb, Ta, (with high Nb/Ta
It is noteworthy that the dark colored zones or bands
- ratios, ranging between 5 and 20), Ti, FeO* and lower
in cassiterite of lithium albite granites are characteristi-
- Ga2O3 (<0.01 wt%.). The level of enrichment in the ele-
cally deep orange to reddish brown whereas, the dark
- - ments Nb, Ta, Ti and Fe in cassiterite of apogranites is
zones in cassiterite of apogranites are typically brown to much less than that of the lithium albite granites. As,
even black. mentioned before, this cassiterite is characterized by the
Cassiterite crystals disseminated in stanniferous development of brown to even opaque pleochroic color
granites (i.e. metasomatized and lithium albite granitoids) zones which are oscillatory alternating with lighter ones.
commonly exhibit gentle progressive zoning character- The dark zones are characteristically enriched in Nb, Ta,
ized by small scale variations in Nb, Ta, and Fe (Figs. 2A
- Ti, and Fe relative to the lighter ones (Table 1, and Figs.
and 2B). Meanwhile, cassiterite of quartz veins and grei- 3 5).
-
sen bodies is distinguished by the development of oscilla- The collective trends exhibited by Ti, Fe*, Nb, and
tory zoning. Ta are in contrast to those exhibited by Sn (Fig. 3). The
Sector zoning is displayed as colored parts which are trends reveal that Sn is substituted by Ti, Fe*, Nb, and Ta
confined to crystal’s acute termination. Such phenomenon in the cassiterite structure. This is reascertained in Fig-
can be detected where the {100} growth sectors of cassit- ures. 4 and 5. It is clear that the reddish and dark color
erite can incorporate greater concentrations of distinct zoning displayed by cassiterites is directly related to the
trace elements (e.g., Nb, Ta, Ti and Fe) relative to {110} substitution of Nb5+, Ta5+, Fe2+ and Ti4+ for Sn4+ in the cas-
sectors. siterite lattice structure.
The color and pleochroism (and hence the chemis-
try) of cassiterite vary among the different modes of oc- DISCUSSION
currences (i.e., disseminated, greisens and quartz veins).
The present study is focused upon the detection of color During magmatic fractionation, tin occurs as Sn4+ either
variation and zoning styles of the cassiterite associated isomorphously substituting for Ti4+, Fe3+ and Mg2+ in their
with the two distinguished types of stanniferous granit- minerals, particularly biotite (Groves and McCarthy,
oids (i.e. metasomatized and lithium albite granitoids). 1978) or complexed by strong ligands such as F– and Cl–.
Cassiterite precipitates under conditions of where by vola-
CASSITERITE CHEMISTRY tiles are vaporized according to the reaction:
Cassiterite, SnO2, has a tetragonal lattice structure similar SnF4 + 2H2O → 4HF↑ + SnO2 (cassiterite)↓ (1).
to that of rutile, belonging to the p42/mnm space group,
in which a cation is in sixfold coordination with oxygen. Heinrich (1995) has proposed three mechanisms re-
The radius ratio, RMetal/Roxygen, in this isostructural group sponsible for cassiterite deposition. The first is vapor sep-
of minerals lies between the limits of 0.732 and 0.414 aration due to boiling which effectively removes HCl and
324 H.M. Abdalla, H. Matsueda, M.A. Obeid and R. Takahashi
Figure 3. Sn versus Nb, Ta, Fe* (total Fe as Fe2+) and Ti variation diagrams for the investigated cassiterite in stanniferous granitoids, Egypt. The
element contents are in atom/formula.
HF and hence causes the precipitation of cassiterite. The such a granitic association. Nb is usually more abundant
second is the mixing of hot saline magmatic melt with than Ta in crustal rocks (the average crustal contents of
non magmatic fluid during the emplacement of granites
- Nb and Ta are 0.002% and 0.0025%, respectively;
and subsequent metasomatic process. The third mecha- Smirnov et al., 1983). The Nb/Ta ratios in rare metal -
nism is the acid neutralization by feldspar hydrolysis that granitoids showing alkaline affinity are also high (Raim-
takes place during the greisenization process. bault et al., 1991). Abdalla et al. (1998) have termed the
Rudorff and Luginsland (1964) have reported the lithium albite granitoids (e.g., Abu Dabbab and Igla) as
presence of complete solid solutions between Nb2O and Ta granites as they are characterized by a high content of
-
TiO2 with an ordered rutile structure. Since rutile and cas- Ta and extremely low Nb/Ta ratios ranging between 0.30
siterite are isostructural, it may be reasonable to assure and 2.0.
that TaO2 and NbO2 behave similarly in both the two lat- Figures 3 5 indicate that Nb and Ta in the cassiterite
-
crease crystal growth (Allegre et al., 1981). Also, abrupt acterized by development of a deep orange to reddish
-
changes in the diffusion rates of some elements (e.g., Nb, brown pleochroic core or bands which are rimmed or os-
Ta, Ti and Fe) might have occurred, most probably due to cillatory alternate with lighter bands.
rapid addition of new fluid to the system. The conspicuous variation in colors, pleochroism
It is noteworthy, that the conspicuous variation in the and chemistry of cassiterite from metasomatized apogran-
colors, pleochroism and chemistry of cassiterite from ites and lithium albite granites can be considered as a
metasomatized apogranites and lithium albite granites can valuable exploration tool when prospecting for primary
be considered as a valuable exploration tool when pros- cassiterite mineralization. Thus, during the panning sur-
326 H.M. Abdalla, H. Matsueda, M.A. Obeid and R. Takahashi
vey, which is largely applied to rare metal mineralizations Helba, H., Trumbull, R.B., Morteani, G., Khalil, S.O. and Arslan,
in general and cassiterite deposits in particular (where A. (1997) Geochemical and petrographical studies of Ta min-
eralization in the Nuweibi albite granite complex, Eastern
cassiterite is essentially dispersed in mechanical aureoles), Desert, Egypt. Mineralium Deposita, 32, 164, 179.
the pleochroism of any cassiterite present indicates the Hurlbut, JR. and Klein, C. (1979) Manual of mineralogy. pp. 532,
nature of the primary mineralizations (i.e., magmatic or John Wiley and Sons.
metasomatic). Kovalenko, V.I. and Kovalenko, N.I. (1984) Problems of the ori-
gin, ore-bearing and evolution of rare-metal granites. Physics
Earth Planet. Interiors, 35, 51-62.
ACKNOWLEDGMENT Moller, P., Dulski, P., Szacki, W., Malow, G. and Riedel, E. (1988)
Substitution of tin in cassiterite by tantalum, niobium, tung-
We are indebted to Mr. Mahmoud Higazy for his assis- sten, iron and manganese. Geochimica et Cosmochimica
tance in the layout of figures. Acta, 52, 1497-1503.
Mohamed, F.H., Abdalla, H.,M. and Helba, H. (1999) Chemistry
of micas in rare-metal granitoids and associated rocks, East-
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