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4 AUTHORS, INCLUDING:
Encarnacion Roda-Robles
Alfonso Pesquera
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ABSTRACT
The Caada pegmatite (Salamanca, Spain), a Li-P-(Sn-Nb Ta)-bearing granitic pegmatite, is
intruded partly into a gabbro and partly into a leucogranite. Three phosphate associations have been
distinguished, based on paragenesis, texture, and chemistry: (1) ferrisicklerite-magniotriplite-johnsomervilleite association (in the border zone), in which Mg-bearing phosphates and coexisting Fe-Mg
silicates are abundant; (2) ferrisicklerite-graftonite association (in the transition zone) characterized
by higher values of Fe/(Fe + Mg) than in the border zone; and (3) triphylite-sarcopside association (in
an inner zone), which also includes minor montebrasite, ferrocolumbite, and cassiterite, typical of an
evolved pegmatite facies. As a result of the decrease of Mg, the Fe/(Fe + Mg) ratios for phosphates,
biotite, and tourmaline increase from the border to the inner association (e.g., for ferrisicklerite and
graftonite, from 0.67 and 0.85 in the border to 0.94 and 0.98 in the inner association, respectively).
This difference is particularly evident for biotite and tourmaline; for example, the Fe/(Fe + Mg) ratios
for tourmaline range from 0.59 in the border to 0.86 in the inner zone. These variations seem to reflect
contamination of marginal zones of the pegmatite by some type of reaction with the host gabbro. Thus,
an evolutionary trend involving inward crystallization from the margins and contamination of fluids
from wallrocks into pegmatite-forming melt may be a plausible genetic model. The occurrence of
phosphates along with Fe-Mg silicates would indicate that the melt contained on the order of 1.32.4
wt% P2O5, based on experimental silicate-phosphate equilibria.
INTRODUCTION
Many Li P Sn NbTa-bearing granitic pegmatites
occur in the western part of the provinces of Salamanca and
Zamora (Spain). Most of these rare-element pegmatites have
been studied previously, and include the Fregeneda pegmatite
field (Martn-Izard et al. 1992; Roda et al. 1996, 1999), the Pinilla de Fermoselle pegmatite (Martn-Izard et al. 1992; Roda et
al. 1998), the Castillejo de dos Casas-Barquilla pegmatites and
montebrasite-bearing quartz dikes (Martn-Izard et al. 1992), and
the Golpejas Sn-Nb-Ta-Li-bearing albititic leucogranite (MartnIzard et al. 1992). Phosphates of Fe-Mn or Li-Al occur in all
these pegmatites, and their study has helped to establish both
the degree of evolution and the petrogenesis of these pegmatitic
bodies (Roda et al. 1996, 1998).
In the southeast part of this region (Fig. 1), the Li-P-(SnNbTa)-bearing Caada pegmatite crops out, intruded partially
into a small gabbroic body and in part into a leucogranite. Although the Caada pegmatite has been described previously by
Martn-Izard (1979) and Martn-Izard et al. (1992), and the occurrence of an Li-Fe-Mn phosphate was noted, recent investigations
by the present authors have revealed the presence of complex
associations of primary Mn-Fe Mg Li-bearing phosphates.
Because many of these phosphate minerals probably are unfamiliar to some readers, a comprehensive listwith formulaeis
provided here in Table 1.
The presence of three different phosphate assemblages with
different degrees of evolution in the Caada pegmatite allow
* E-mail: npproroe@lg.ehu.es
0003-004X/04/0001110$05.00
110
GEOLOGICAL SETTING
The Caada pegmatite is located in the midwestern part of
the province of Salamanca, in the Central Iberian Massif (CIM).
Hercynian granites are widespread in this area and can be divided
into two main groups: (1) pre- to syntectonic, peraluminous,
locally two-mica leucogranites; and (2) undeformed granitoids,
mainly subporphyritic, K-feldspar-rich granodiorites. The
leucogranite intruded partly by the Caada pegmatite, a pre- to
syntectonic, two-mica, alkaline leucogranite, belongs to the first
group. This leucogranite corresponds to a very evolved facies,
containing garnet and tourmaline as common accessory minerals
(Martn-Izard et al. 1992). The leucogranites are strongly
peraluminous, with ASI 1.35 [ASI being the Al2O3/(CaO +
111
Formula
Border Z.
Primary phosphates
triphylite
graftonite
wolfeite
ferrisicklerite
manganoan fluorapatite
magniotriplite
johnsomervilleite
xenotime-Y
montebrasite
Exsolution phosphates
sarcopside
Association
Transition Z.
Inner Z.
o
++
o
++++
++
+++
++
+
o
o
+++
o
++++
+
o
o
+
+
++++
++
+
+
o
o
o
o
+
(Fe2+,Mn2+)3(PO4)2
+++
2+
2+
Secondary phosphates
alluaudite
(Na,Ca) 2-1Mn2+ (Fe3+)2(PO4)3
++
++
hagendorfite
Na2Mn2+ (Fe2+,Fe3+)2(PO4)3
++
++
3+
2+
2+
stankite
Fe (Mn ,Fe ,Mg)(PO4)O
++
++
arrojadite
KNa4Ca(Fe2+,Mn2+,Mg)14Al(PO4)12(OH,F)2
o
o
2+
2+
ABP1
Ca9(Fe ,Mn )4Al2(PO4)10(OH)2
o
o
2+
huraulite
Mn5 (PO4)2[PO3(OH)]24H2O
o
+
2+
2+
eosphorite
(Mn ,Fe )Al(PO4)(OH)2H2O
o
+
barbosalite
Fe2+Fe23+(PO4)2(OH)2
o
o
2+
2+ 2+
3+
rockbridgeite
(Fe ,Mn ) Fe 4(PO4)3(OH)5
+
+
2+
2+
3+
jahnsite s.l.
CaMn (Mg,Fe )2Fe 2(PO4)4(OH)28H2O
o
o
vivianite
Fe32+(PO4)2.8H2O
o
o
2+
2+
ABP2
CaMn Fe (PO4)2(OH)2H2O
o
+
2+
2+
gormanite-souzalite
(Fe ,Mg)3(Al,Fe )4(PO4)4(OH)62H2O
o
+
leucophosphite
KFe22+ (PO4)2(OH)2H2O
+
+
2+
2+
mitridatite
Ca3(Fe ,Mn )4(PO4)4(OH)63H2O
o
o
2+
2+
whiteite s.l.
Ca(Fe ,Mn )Mg2Al2(PO4)4(OH)28H2O
+
+
2+
2+
fairfieldite
Ca2(Mn ,Fe )(PO4)22H2O
o
o
collinsite
Ca2(Mg,Fe2+)(PO4)22H2O
+
o
2+
2+
reddingite
(Fe Mn )3(PO4)23H2O
o
o
crandallite
CaAl3(PO4)2(OH)5H2O
+
+
fluorapatite
Ca5(F,OH)(PO4)3
o
o
Note: The abundance in each association is given as: ++++ = abundant, +++ = common, ++ = rare, + = very rare, o = absent.
++
++
+
+
+
++
+
+
++
+
+
o
++
o
+
++
+
o
+
o
+
112
magniotriplite, johnsomervilleite, manganoan fluorapatite, xenotime-(Y), and silicates such as garnet, tourmaline, and biotite.
Ideal formulae and abundances are given in Table 1, and the main
petrographic characteristics are summarized in Table 2.
Primary phosphates. Ferrisicklerite is the most abundant
phosphate in the border zone of the pegmatite, appearing in
masses up to 15 cm in length. Although the primary character
of ferrisicklerite is not accepted by all authors (due to the oxidized
state of Fe in this phosphate), no relict of a previous triphylite
has been found in any of the more than one hundred thin sections
examined. Consequently, petrographic evidence encourages us
to regard ferrisicklerite in the border zone as a primary phase, as
it has been described previously in other phosphate assemblages
(Corbell and Melgarejo 1990; Roda et al. 1996, 1998). In addition, the existence of Fe3+ is documented by the occurrence
of primary associations of Li-Fe-Mn phosphates and hematite,
which are abundant in some pegmatites (e.g., Hagendorf-Sud,
Bavaria, and New Hampshire). Additionally, the primary paragenetic intergrowth of magnetite + triplite has been described by
Keller and Von Knorring (1989). In the Caada pegmatite, the
petrographic textures suggest that ferrisicklerite is coeval with
Fe-Mg silicates, and that it is replaced by graftonite, alluaudite,
and stankite. Ferrisicklerite from the border zone contains
an average MgO content of 7.5 wt%. One individual analysis
showed 11.7 wt% MgO, the highest amount known for natural
ferrisicklerite (Table 4, Fig. 2a).
Magniotriplite is found only within the border zone. It appears
as fine-grained anhedral to subhedral crystals that form nodular
aggregates up to 8 cm long (Table 2, Fig. 3a). Recrystallization
textures, characterized by undulatory extinction and subgrains,
are common in the magniotriplite. Alteration products of magniotriplite include alluaudite, stankite, and less commonly, rockbridgeite (Fig. 3a). Magniotriplite usually has been described
as a primary phase, even earlier than triphylite, although some
exceptions have been reported (Keller et al. 1994). In the Caada
pegmatite, magniotriplite appears to be primary and is associated
with manganoan fluorapatite, johnsomervilleite, and ferrisicklerite. In general, the Mg content is very heterogeneous with mean
MgO values of 15.5 wt% (Table 4, Fig. 2a), with some samples
containing up to 30.0 wt% MgO. In contrast to ferrisicklerite,
where Mn values remain more or less constant, a negative correlation between the Mg and the Mn contents is observed in
magniotriplite. This negative correlation is less clearly developed
for Mg and Fe. Concentrations of CaO are less than 0.3 wt%,
whereas (mean) concentrations of F and TiO2 are ~3.8 wt% and
~0.5 wt%, respectively (Table 4).
Johnsomervilleite, like magniotriplite, is restricted to the
border zone of the pegmatite. According to petrographic data
(Table 2), it is a primary phase in this assemblage, and commonly
appears as subhedral to globular fine-grained crystals, together
with graftonite and ferrisicklerite, exhibiting a granoblastic
texture (Fig. 3b). Johnsomervilleite usually displays an orange
rim with the same composition as the inner zone of the grain.
It may be partially altered into stankite. The mean Fe/(Fe +
Mn) ratio for johnsomervilleite is ~0.55 (Table 4, Fig. 2a). The
Fe/(Fe + Mg) ratio ranges from 0.53 to 0.66, with MgO contents
over 6.8 wt%.
Although manganoan fluorapatite also occurs in the transition
113
TABLE 2. Main petrographic characteristics of the minerals from the border zone and the transition zone associations
Assoc.
Mineral
Habit and
textures
Grain size
*
Fe/
(Fe+Mg)
Main mineral
association
Border
Zone
Primary phosphates
Ferrisicklerite
granoblastic and
interlayered textures,
fine to
coarse
0.550.70
Magniotriplite
granoblastic texture
an- to subhedral habit
fine
to coarse
0.270.58
fsck-Mn-apt
stnk, rckb, grn, bio, tour
Johnsomervilleite
granoblastic texture
an- to subhedral habit
very fine
to fine
0.530.66
fsck-grft
stnk, grn, bio, tour
Manganoan fluorapatite
fine
to coarse
>0.65
fsck-xntm
mgtr
Xenotime-Y
very fine
Mn-apt, fsck
Graftonite
granoblastic texture
an- to subhedral habit
very fine
to medium
0.0.850.89
fsck-jhsm
stnk
Secondary phosphates
Alluaudite
0.540.79
fsck, stnk
Stankite
anhedral habit
0.690.78
Silicates
Garnet
fine to
medium
0.900.98
Muscovite
subhedral habit
fine to coarse
0.63
Biotite
subhedral habit
fine to medium
0.68
Tourmaline
subhedral habit
fine to coarse
0.59
Oxides
Corundum
subhedral habit
rounded to irregular,
very fine
musc, bio
granoblastic and
graphic textures,
fine to
coarse
0.720.90
Graftonite
very fine
to medium
0.940.96
fsck, stnk
qz, tour, bio
Mn-apatite
granoblastic texture
an- to euhedral habit
fine
to medium
>0.93
fsck
xntm
Xenotime
very fine-
Secondary phosphates
Alluaudite
0.750.91
fsck, stnk
Stankite
anhedral habit
very fine
0.880.93
fsck, grft
Silicates
Muscovite
subhedral habit
fine to medium
tour,bio,fsck,grft,mtbr,eosp
graphic texture
an- to subhedral habit
fine to
medium
0.86
Transition
Zone
Primary phosphates
Ferrisicklerite
Biotite
Mn-apt, fsck
Tourmaline
graphic texture
fine to
0.74
bio, qz,
an- to euhedral habit
medium
grft, fsck
Notes: Abreviations: ferrisicklerite = fsck; alluaudite = allu; montebrasite = mtbr; huraulite = hur; stankite = stnk; gormanite-souzalite = grm; manganoan fluorapatite = Mn-apt; xenotime-Y = xntm; magniotriplite = mgtr; johnsomervilleite= jhmv; whiteite = whit; hureaulite = hur; rockbridgeite = rckb; leucophosphite =
lcp; crandallite = crd; montebrasite = mtbr; eosphorite = eosp; collinsite = coll; muscovite = musc; biotite = bio; tourmaline = tour; garnet = grn; cassiterite = cass;
columbite-tantalite = col; uraninite = ura; corundum = cor; quartz = qz. * grain size: very fine = < 1 mm; fine = 1 to 5 mm; medium = 5 mm to 2.5 cm; coarse = >
2.5 cm.
zone, the mean MnO content of the apatite is ~5.8 wt%, which
is slightly higher than in the transition zone (Table 4). There is
a certain positive correlation between Fe and Mn, as has been
described previously for other apatites in this region (Roda et al.
1996). The average content of F is ~2.5 wt%; a relation between
114
TABLE 3. Main petrographic characteristics of the minerals from the inner zone association
Mineral
Habit and
textures
Grain size
*
Fe/
(Fe+Mg)
Main mineral
association
granoblastic texture
anhedral habit
fine to
coarse
0.910.95
Graftonite
granoblastic texture
0.98
fsck srcp
Wolfeite
anhedral habit
very fine
0.920.96
trph srcp
Montebrasite
Exsolution phosphates
Sarcopside
lamellar, twinned
fine to medium
0.960.97
Secondary phosphates
Ferrisicklerite
granoblastic texture
fine to medium
0.93-0.96
Alluaudite
0.880.97
Barbosalite
0.940.99
Hureaulite
very fine
to fine
very fine
to fine
very fine
to fine
very fine to fine
0.700.99
Stankite
0.930.97
Gormanite-souzalite
anhedral habit
0.910.94
trph, srcp
Silicates
Plagioclase
Muscovite
subhedral
tabular habit
fine to mdium
fine to coarse
0.86
trphsrcp
trphsrcp
Biotite
subhedral habit
Tourmaline
fine
0.86
trphsrcp
Oxides
Cassiterite
subhedral habit
fine to medium
Ferrocolumbite
tabular habit
fine to medium
Uraninite
rounded habit
very fine
Primary phosphates
Triphylite
ABP1
Arrojadite
0.970.98
0.88
(Table 3, Fig. 2a). This ratio is even lower than that reported
by ern et al. (1998) for graftonites associated with a simple
barren pegmatite that is, apparently, the petrogenetically least
evolved magmatic environment ever to yield graftonite. Similar
to the present case, graftonite in the border zone appears with
biotite and garnet, and is in close association with johnsomervilleite, which commonly appears as globular small crystals inside
coarser graftonite. Graftonite also replaces ferrisicklerite along
the grain boundaries, and where the replacement is extensive,
small relict inclusions of ferrisicklerite are present.
Secondary phosphates. The replacement of ferrisicklerite by
alluaudite shows similar characteristics to some examples in the
literature (Huvelin et al. 1972; Fransolet et al. 1986; Keller and
Von Knorring 1989; Roda et al. 1996, 1998). When the replacement is incipient, it follows crystallographic directions giving
rise to a grid of deep yellow color. In many cases, ferrisicklerite
exhibits slightly pleochroic patches of yellow to light-brownish
115
116
TABLE 4. Chemical compositions* of the main phosphates from the border zone association
N
P2O5
Al2O3
TiO2
Fe2O3
FeO
MnO
MgO
ZnO
CaO
K2O
Na2O
F
Cl
Total
jhmv
65
41.04
0.01
0.00
n.a.
20.68
16.85
6.88
0.11
4.01
0.05
5.38
n.a.
n.a.
95.02
18.000
Al
Fe2+
Mn
Mg
Zn
Ti
Ca
0.007
8.970
7.413
5.325
0.030
0.000
21.745
0.255
22.000
X
CaVIII
NaVIII
Na
K
"Na"
P2O5
Al2O3
TiO2
Fe2O3
FeO
MnO
MgO
ZnO
CaO
K2O
Na2O
F
Cl
Total
mgtr
68
34.39
0.04
0.49
0.00
26.50
15.70
15.46
0.08
0.25
0.02
0.04
3.84
0.00
92.97
O=F
Total
1.61
91.36
fsck
57
46.28
0.01
0.00
30.03
0.00
9.12
7.49
0.09
0.41
0.07
0.28
0.00
0.00
93.78
Mn-apt
29
40.47
0.01
0.00
0.00
1.48
5.76
0.25
0.00
48.42
0.00
0.21
2.53
0.24
99.38
grft
38
39.83
0.01
0.00
0.00
24.88
20.62
2.05
0.13
10.47
0.02
0.06
n.a.
n.a.
99.56
stnk
23
32.29
0.01
0.07
38.25
0.00
16.15
6.65
0.16
0.50
0.11
0.28
n.a.
n.a.
94.46
1.06
98.32
1.000
1.000
6.000
2.000
1.000
1.986
1.014
Al
Ti
Fe3+
Fe2+
Mn
Mg
Zn
Ca
K
0.002
0.013
0.000
0.766
0.459
0.784
0.002
0.009
0.001
0.000
0.000
0.577
0.000
0.199
0.285
0.001
0.011
0.003
0.001
0.000
0.000
0.217
0.854
0.065
0.000
9.083
0.001
0.001
0.000
0.000
1.234
1.037
0.089
0.007
0.666
0.002
0.000
0.002
1.055
0.000
0.500
0.362
0.004
0.020
0.005
3.000
Na
0.002
0.014
0.071
0.007
0.020
4.404
0.030
4.434
F
Cl
0.414
0.000
1.402
0.073
Fe/(Fe+Mn)
0.548
Fe/(Fe+Mg)
0.499
0.670
0.770
0.933
0.741
Fe/(Fe+Mg)
0.629
Fe/(Fe+Mn)
0.623
0.746
0.202
0.543
0.757
Fe/(Fe+Mg+Mn)
0.414
Fe/(Fe+Mn+Mg)
0.382
0.545
0.191
0.523
0.548
Notes: Data obtained by EMPA techniques. * abreviations as in Table 2. The cation numbers are calculated on the basis of 16PO4 per unit cell for johnsomervilleite;
2PO4 per unit cell for graftonite, 1PO4 per unit cell for ferrisicklerite, magniotriplite and stankite, and 6PO4 per unit cell for manganoan fluorapatite. N = number
of points of analyses. n.a. = not analized
TABLE 5.
P2O5
CaO
Y2O3
La2O3
Ce2O3
Nd2O3
Sm2O3
Gd2O3
Tb2O3
Dy2O3
Ho2O3
Er2O3
Tm2O3
Yb2O3
Total
Y
3.120
La
0.000
Ce
0.000
Nd
0.010
Sm
0.036
Gd
0.193
Tb
0.035
Dy
0.279
Ho
0.046
Er
0.133
Tm
0.012
Yb
0.111
Ca
0.045
P
4.051
*Data obtained by EMPA techniques.
117
FIGURE 3. Photomicrographs of some textures in the border zone association (a, b, c, d, and e), and in the transition zone association (f):
(a) tourmaline (tour) with granoblastic manganoan fluorapatite (Mn-apt) and magniotriplite (mgtr), which is partially replaced by fan-shaped
rockbridgeite (rckb); (b) rounded crystals of johnsomervilleite (jhsm) inside ferrisicklerite (fsck), which is replaced by graftonite (grft) and stankite
(stnk) in places; (c) striped intergrowth of manganoan fluorapatite (Mn-apt) and ferrisicklerite (fsck), together with euhedral crystals of xenotime-Y
(xntm); (d) granoblastic ferrisicklerite (fsck) partially replaced by alluaudite (allu) and stankite (stnk), together with garnet (grn) and quartz (qz);
(e) crystal of muscovite (musc) partially replaced by corundum (cor) and biotite (bio); and, (f) graphic intergrowth with ferrisicklerite (fsck) and
graftonite (grft), together with quartz (qz) and biotite (bio). (All photomicrographs in plane-polarized light. Scale for a, b, c, d, and f = 1.8 2.6
mm. Scale for e = 0.4 0.6 mm).
118
10
45.09
0.01
21.43
8.54
10.38
0.03
1.20
0.03
9.58
96.29
10
44.11
0.01
25.71
12.44
5.13
0.09
0.33
0.16
7.80
95.77
Transition Zone
5
9
43.61
43.13
0.00
0.01
22.01
30.50
16.90
11.95
3.98
2.00
0.05
0.09
1.06
0.93
0.07
0.09
8.24
6.24
95.94
94.93
Inner Zone
3
42.70
0.14
23.40
19.51
0.87
0.05
2.27
0.36
6.75
96.04
5
42.96
0.02
33.40
10.07
1.15
0.15
0.13
0.11
9.00
96.99
M2
Al
Fe3+
Mg
Fe++
Zn
Mn
0.003
3.793
4.197
0.000
0.007
0.000
8.000
0.003
5.339
2.459
0.178
0.021
0.000
8.000
0.000
4.911
1.928
1.071
0.013
0.077
8.000
0.004
5.951
0.977
1.045
0.023
0.000
8.000
0.055
4.907
0.430
1.588
0.011
1.009
8.000
0.007
4.890
0.566
2.500
0.037
0.000
8.000
M1
Mg
Fe2+
Mn
Ca
0.665
1.840
1.495
0.000
4.000
0.000
1.391
2.609
0.000
4.000
0.000
0.000
4.000
0.000
4.000
0.000
1.386
2.614
0.000
4.000
0.000
0.000
4.000
0.000
4.000
0.000
1.826
2.174
0.000
4.000
X1
Fe2+
Mn
Ca
Na
0.000
0.779
0.405
2.816
4.000
0.000
0.776
0.113
3.111
4.000
0.000
0.575
0.370
3.055
4.000
0.000
0.711
0.327
2.962
4.000
0.000
0.476
0.806
2.718
4.000
0.000
0.641
0.045
3.314
4.000
X2
Ca
Na
K
0.000
3.025
0.012
0.963
4.000
0.000
1.747
0.065
2.188
4.000
0.000
2.137
0.030
1.833
4.000
0.000
1.013
0.037
2.950
4.000
0.000
1.628
0.152
2.220
4.000
0.000
2.444
0.046
1.510
4.000
Fe/(Fe + Mg)
0.537
0.737
0.756
0.896
0.938
0.942
Fe/(Fe+Mn)
0.712
0.671
0.563
0.716
0.542
0.766
Fe/(Fe+Mn+Mg)
0.441
0.542
0.476
0.661
0.523
0.732
Notes: Number of cations on the basis of 12(PO4). The structural formulae are calculated following the procedure suggested by Moore (1971). Fe3+ calculated by
stoichiometry. N = number of points of analyses.
* Data obtained by EMPA techniques.
wolfeite-triploidite series (Fig. 2c). Montebrasite is closely related to triphylite, and appears as fine-grained crystals showing
polysynthetic twinning.
Exsolution phosphates. Like triphylite, sarcopside is only
found in the inner zone of the pegmatite, where it commonly
appears as lenticular or irregular lamellae (up to 1 cm long and
3 mm thick) within triphylite (Fig. 4a), and locally within ferrisicklerite. In both cases, sarcopside is typically twinned. It
also appears as narrow rims around granoblastic ferrisicklerite
crystals, intergrown with graftonite (Figs. 4d and 4e). Where
triphylite is altered to barbosalite, hureaulite, and whiteite,
sarcopside is entirely replaced by these secondary phosphates,
and the primary lamellar texture is absolutely overprinted by a
cellular one. Although graftonite is present in the inner zone of
the pegmatite, in contrast to many other phosphate assemblages,
sarcopside lamellae within graftonite have not been observed.
Electron microprobe analyses of eighteen lamellae (seven within
ferrisicklerite), do not show significant variations in composition
(Table 10, Fig. 2c). The Fe/(Fe + Mn) ratio is ~0.80, which is
similar or slightly lower than that of the host triphylite and ferrisicklerite, whereas the Fe/(Fe + Mg) ratio of ~0.96 is slightly
higher than that of the triphylite host.
N
SiO2
TiO2
Al2O3
MgO
CaO
MnO
FeO
Na2O
K2O
Cr2O3
Cl
NiO
ZnO
F
Total
O=F
Total
TABLE 8.
N
SiO2
TiO2
Al2O3
Cr2O3
FeO
MnO
MgO
CaO
Na2O
K2O
Total
Musc
Border Z. Inner Z.
14
7
44.53
44.97
1.08
0.08
33.47
34.33
0.64
0.19
0.01
0.02
0.12
0.13
1.92
2.20
0.52
0.55
10.58
10.52
0.01
0.02
0.01
0.02
0.01
0.03
0.04
0.05
0.10
0.22
93.05
93.34
0.04
93.00
Biot
Border Z. Transition Z.
13
6
31.55
32.99
1.39
0.61
17.25
19.40
6.47
2.63
0.62
0.21
0.85
0.33
24.73
29.31
0.13
0.05
7.93
8.38
0.01
0.00
0.04
0.00
0.02
0.04
0.09
0.17
0.27
0.07
91.33
94.18
0.09
93.25
0.11
0.03
91.22
94.15
continued next column
Transition Z.
14
35.91
0.12
32.69
0.02
12.62
0.15
2.54
0.07
1.97
0.03
86.12
Inner Z.
8
35.62
0.00
32.08
0.01
15.17
0.14
1.34
0.04
1.87
0.04
86.31
Si
Al T
5.991
0.009
6.013
0.000
6.032
0.000
Al Z
6.000
6.000
6.000
Al Y
Ti
Cr
Fe2+
Mn
Mg
Y total
0.421
0.077
0.001
1.395
0.021
0.961
2.799
0.453
0.015
0.002
1.770
0.021
0.632
2.879
0.406
0.000
0.001
2.149
0.020
0.338
2.914
Ca
Na
K
X total
0.011
0.650
0.008
0.669
0.013
0.641
0.006
0.661
0.007
0.613
0.008
0.628
Fe/(Fe+Mg)
0.592
0.735
0.864
Fe//Fe+Mn)
0.985
0.987
0.991
Fe/(Fe+Mg+Mn)
0.587
0.728
0.857
Na/(Na+Ca)
0.983
0.980
0.989
Notes: Number of ions on the basis of 22 oxygens equivalents. N = number of
points of analyses.
* Data obtained by EMPA techniques.
Secondary phosphates. Ferrisicklerite is a common secondary phosphate in the inner zone, where it appears as a minor
costituent. It replaces earlier triphylite following the QuenselMason sequence (see Quensel 1937; Mason 1941). Ferrisicklerite
commonly occurs with graftonite to form granoblastic textures
(Figs. 4d and 4e). Microprobe analyses of ferrisicklerite reveal
low MgO contents, with a mean value of 1.25 wt%, and Fe/(Fe
+ Mg) ratios of ~0.94, whereas the Fe/(Fe + Mn) ratio ~0.81 is
119
TABLE 7.continued
Si
AlIV
Z total
Musc
Border Z.
6.116
1.884
8.000
Inner Z.
6.144
1.856
8.000
Biot
Border Z. Transition Z.
5.194
5.339
2.806
2.661
8.000
8.000
AlVI
Ti
Cr
Fe
Mn
Mg
Zn
Ni
Y total
3.531
0.113
0.001
0.222
0.014
0.131
0.004
0.001
4.018
3.668
0.008
0.003
0.252
0.016
0.039
0.005
0.003
3.996
0.534
0.177
0.001
3.427
0.119
1.577
0.011
0.002
5.848
1.042
0.073
0.000
3.971
0.045
0.634
0.020
0.005
5.790
Ca
Na
K
X total
0.001
0.138
1.855
1.993
0.003
0.144
1.835
1.981
0.109
0.041
1.667
1.816
0.036
0.015
1.729
1.780
Cl
F
0.001
0.045
0.005
0.095
0.010
0.138
0.001
0.038
Fe/(Fe+Mg)
0.627
0.862
0.681
0.861
Fe/(Fe+Mn)
0.946
0.943
0.967
0.989
Fe/(Fe+Mg+Mn)
0.605
0.822
0.665
0.853
Notes: Number of ions on the basis of 22 O atoms equivalents. N = number of
points of analyses.
* Data obtained by EMPA techniques.
TABLE 9.
*
N
P2O5
Al2O3
Fe2O3
FeO
MnO
MgO
ZnO
CaO
K20
Na2O
F
Cl
TOTAL
grft
40
39.56
0.01
n.a.
30.09
18.69
0.90
0.23
8.38
0.20
0.09
n.a.
n.a.
99.56
F=O
Total
Mn-apt
13
41.14
0.02
n.a.
0.53
4.60
0.01
n.a.
50.65
0.01
0.09
3.23
0.04
100.31
stnk
7
31.24
n.a.
46.75
0.00
16.47
2.63
0.30
0.28
0.11
0.17
n.a.
n.a.
97.95
1.36
98.95
1.000
2.000
6.000
1.000
Al
Fe3+
Fe2+
Mn
Mg
Zn
0.000
0.733
0.230
0.129
0.000
0.001
1.504
0.946
0.080
0.007
0.003
0.077
0.671
0.003
1.330
0.528
0.148
0.008
Ca
K
Na
0.006
0.008
0.006
0.536
0.015
0.010
9.348
0.001
0.031
0.011
0.005
0.013
F
Cl
1.758
0.011
Fe/(Fe+Mg)
0.847
0.853
0.961
0.901
Fe/(Fe+Mn)
0.757
0.532
0.102
0.779
Fe/(Fe+Mn+Mg)
0.669
0.487
0.102
0.663
Notes: Abreviations as in Table 2. The cation numbers are calculated on the
basis of 2PO4 per unit cell for graftonite, 1PO4 per unit cell for ferrisicklerite and
stankite, and 6PO4 per unit cell for manganoan fluorapatite. N = number of
points of analyses. n.a. = not analized.
* Data obtained by EMPA techniques.
120
TABLE 10. Chemical compositions* of the main phosphates from the inner zone association
N
P2O5
Al2O3
TiO2
Fe2O3total
FeOtotal
MnO
MgO
ZnO
CaO
SrO
BaO
K2O
Na2O
F
Total
trph
58
43.09
0.00
0.00
0.00
36.89
8.39
1.39
0.07
0.04
n.a.
n.a.
0.01
0.04
n.a.
89.93
srcp
29
38.34
0.02
0.00
0.00
46.88
11.75
0.95
0.09
0.02
n.a.
n.a.
0.01
0.02
n.a.
98.07
grft
7
38.48
0.01
0.00
0.00
31.45
20.05
0.30
0.27
6.97
n.a.
n.a.
0.01
0.29
n.a.
97.83
wolf
9
31.34
0.00
0.00
0.00
45.16
14.32
2.76
0.14
0.14
n.a.
n.a.
0.01
0.03
n.a.
93.90
fsck
17
43.77
0.01
0.00
41.86
0.00
8.70
1.25
0.05
0.25
n.a.
n.a.
0.05
0.07
n.a.
96.01
stnk
15
31.86
0.01
0.00
51.14
0.00
12.29
1.36
0.30
0.09
n.a.
n.a.
0.01
0.03
n.a.
97.10
F=O
Total
arrj
25
39.30
2.56
0.12
0.00
28.29
12.47
2.32
0.06
1.99
0.00
0.02
2.03
6.71
0.13
96.00
ABP1
7
41.87
5.85
0.00
0.00
10.20
6.50
0.09
0.07
28.45
0.12
0.15
0.09
0.72
0.26
94.36
apt
4
42.67
0.03
0.00
0.00
3.08
3.69
0.08
n.a.
46.89
n.a.
n.a.
0.08
0.16
3.04
100.02
0.05
95.95
0.11
94.25
1.28
98.74
1.000
4.000
2.000
1.000
1.000
1.000
12.000
20.000
6.000
Al
Ti
Fe3+
Fe2+
Mn
Mg
Zn
Ca
Sr
Ba
K
Na
0.000
0.000
0.000
0.847
0.195
0.057
0.001
0.001
0.000
0.002
0.002
0.000
0.000
4.836
1.228
0.175
0.008
0.003
0.001
0.005
0.000
0.000
0.000
1.615
1.042
0.028
0.012
0.458
0.001
0.035
0.000
0.000
0.000
1.423
0.457
0.155
0.004
0.006
0.001
0.002
0.000
0.000
0.851
0.000
0.199
0.050
0.001
0.007
0.002
0.004
0.001
0.000
1.000
0.428
0.385
0.076
0.009
0.005
0.001
0.002
1.090
0.045
0.000
8.531
3.810
1.248
0.000
0.769
0.000
0.003
0.934
4.690
3.892
0.000
0.000
4.813
3.105
0.077
0.030
17.200
0.039
0.033
0.063
0.784
0.006
0.000
0.000
0.427
0.519
0.094
8.346
0.048
0.051
0.145
0.000
1.595
Fe/(Fe+Mg)
0.937
0.965
0.983
0.902
0.944
0.950
0.872
0.984
0.820
Fe/(Fe+Mn)
0.813
0.795
0.608
0.757
0.811
0.827
0.691
0.608
0.452
Fe/(Fe+Mn+Mg)
0.771
0.775
0.601
0.699
0.773
0.758
0.628
0.602
0.411
Notes: The cation numbers are calculated on the basis of 1PO4 per unit cell for triphylite, ferrisicklerite, wolfeite and stankite; 2PO4 per unit cell for graftonite, 4PO4
per unit cell for sarcopside; 12PO4 per unit cell for arrojadite, 20PO2 per unit cell for ABP1, and 6PO4 per unit cell for apatite. N = number of points of analyses. n.a.
= not analyzed.
* Data obtained by EMPA techniques. Abreviations as in Table 3.
TABLE 11. Chemical compositions* of cassiterite, ferrocolumbite and uraninite from the inner zone association
N
Nb2O5
Ta2O5
FeO
MnO
SnO2
TiO2
CuO
Sc2O3
Total
Cassiterite
Dark-brown
reddish-brown
2
4
0.58
0.04
0.47
0.34
0.20
0.06
0.00
0.01
100.48
100.71
0.00
0.16
0.00
0.00
0.00
0.00
101.73
101.33
Ferrocolumbite
2
70.59
0.78
17.01
3.32
0.49
1.73
0.00
0.00
93.91
4
68.04
7.23
16.76
3.79
0.21
1.74
0.00
0.06
97.81
Uraninite
4
62.55
11.05
16.17
3.17
0.47
0.98
0.00
0.00
94.39
ThO2
UO2
Ce2O3
Nd2O3
Gd2O3
Dy2O3
P2O5
PbO
Total
3
0.29
92.49
0.42
0.26
0.39
0.17
0.00
4.75
98.77
Nb
0.006
0.000
1.908
1.811
1.762
Th
0.003
Ta
0.003
0.002
0.013
0.116
0.187
U
0.941
Fe
0.004
0.001
0.851
0.825
0.843
Ce
0.014
Mn
0.000
0.000
0.168
0.189
0.167
Nd
0.008
Sn
0.986
0.993
0.012
0.005
0.012
Gd
0.011
Ti
0.000
0.003
0.078
0.077
0.046
Dy
0.005
Cu
0.000
0.000
0.000
0.000
0.000
P
0.000
Sc
0.000
0.000
0.000
0.003
0.000
Pb
0.055
Mn/(Fe+Mn)
0.165
0.186
0.165
Ta/(Nb+Ta)
0.006
0.060
0.096
Notes: Number of cations on the basis of 2 oxygen atoms for cassiterite and uraninite, and 6 atoms of oxygen for ferrocolumbite. N = number of points of analyses.
* Data obtained by EMPA techniques.
121
122
DISCUSSION
Many descriptions of Fe-Mn phosphate mineral associations
occurring in granitic pegmatites can be found in the literature
(e.g., Fransolet et al. 1986; Keller 1991; Keller and Von Knorring
1989; Roda et al. 1996, 1998; ern et al. 1998; Smeds et al.
1998; Masau et al. 2000). Most of these investigations focused
their attention on paragenetic and compositional aspects of the
phosphate associations. Although the Fe/(Fe + Mn) ratio of some
Fe-Mn phosphates commonly has been used to assess the degree
of evolution of the pegmatites, references to the petrogenetic
role of the phosphates in the evolution of pegmatites are scarce
(e.g., London et al. 1999). In the Caada pegmatite, the Fe/(Fe
+ Mn) ratio remains almost constant throughout the three associations, yet the phosphates and their associated minerals show
petrographic and compositional variations that are consistent
with crystallization inward from the margins. Different lines
of evidence support this interpretation: (1) paragenetic associa-
123
124
ACKNOWLEDGMENTS
The authors are greatly indebted to A. M. Fransolet for its comments and helpful suggestions that have considerably improved the manuscript. We also thank
M. Wise, W.B. Simmons, and J. Nizamoff for their suggestions and their critical
reviews. Review was also provided by P. ern, whose comments are much appreciated. We gratefully acknowledge A. Martn-Izard for his useful comments
on the geology at the area, and for provided information about the mining of the
pegmatitic body. We also thank Ph. de Parseval, who carried out the electron-microprobe analyses at the Universit Paul Sabatier, Toulouse (France).
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