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American Mineralogist, Volume 89, pages 110125, 2004

Phosphate mineral associations in the Caada pegmatite (Salamanca, Spain): Paragenetic

relationships, chemical compositions, and implications for pegmatite evolution
ENCARNACIN RODA,1,* ALFONSO PESQUERA,1 FRANOIS FONTAN,2 AND PAUL KELLER3
1
Departamento de Mineraloga y Petrologa, Univ. Pas Vasco/EHU, Apdo. 644, E-48080 Bilbao, Spain
Laboratoire Cristallographie et Minralogie, URA-067-Univ. Paul Sabatier de Toulouse, Alles Jules-Guesde 39, F-31400, Toulouse, France
3
Institut fr Mineralogie und Kristallchemie, Univ. Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany

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

us to evaluate the role that these phosphate phases play in the

internal evolution of the pegmatite. Moreover, the coexistence of
ferromagnesian silicates such as biotite, garnet, and tourmaline
with Fe-Mn phosphates, provides an opportunity to investigate
the relationships between these two groups of minerals. The
study of these different phosphate-cum-silicate assemblages
can significantly contribute to understanding the petrology of
this pegmatite.
The purpose of this study is twofold. First, we investigate the
exceptional mineralogical features of the pegmatite and give an
interpretation of their paragenetic relationships and chemical
trends. Second, we discuss the abundance and source of P in
the pegmatite-forming magma, which leads us to consider the
influence of the host gabbro on the composition of the different
phosphate associations.

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 +

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

111

TABLE 1. List of phosphate minerals identified in the Caada pegmatite

Mineral name

Formula
Border Z.

Primary phosphates
triphylite
graftonite
wolfeite
ferrisicklerite
manganoan fluorapatite
magniotriplite
johnsomervilleite
xenotime-Y
montebrasite
Exsolution phosphates
sarcopside

Association
Transition Z.

Inner Z.

Li(Fe ,Mn )PO4

(Fe2+,Mn2+,Ca)3(PO4)2
2+
(Fe ,Mn2+,Mg)2(PO4)OH
Li1-x(Fex3+ ,Mn1-x)PO4
(Ca,Mn)5(F,OH)(PO4)3
(Mg,Fe2+,Mn2+,Ca)2(PO4)2(F,OH)
Na2Ca(Fe2+,Mn2+)7(PO4)6
(Y,HREE)PO4
LiAlPO4(F,OH)

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.

FIGURE 1. Schematic geological map of the study area (Salamanca,

Spain). (Modified from Martn-Izard et al. 1992.)

Na2O + K2O) molar ratio] in the most evolved, tourmaline- and

garnet-bearing facies, whereas their P2O5 contents range from
0.15 to 0.29 wt% (Martn-Izard 1979). Besides the granitic
bodies, small stocks of mafic and ultramafic composition crop out
throughout the region, and predate the granitoids with which they
are associated spatially (Department of Petrology, University of

++
++
+
+
+
++
+
+
++
+
+
o
++
o
+
++
+
o
+
o
+

Salamanca, 1980). The Caada pegmatite also intrudes partly into

one of those pre- to syntectonic biotite-bearing gabbro bodies.
The gabbro is rounded in outcrop with a diameter of ~100
m, and forms a very large enclave within the aforementioned
leucogranite (Fig. 1) (Martn-Izard et al. 1992). The gabbro
consists of biotite, hornblende, augite, and calcic plagioclase.
Near the contact with the pegmatite, the gabbro shows extensive
alteration, with albitization of plagioclases, and cloritization of
ferromagnesian minerals.
The granitic plutons and the mafic and ultramafic rocks
intruded Precambrian and Cambrian metasedimentary rocks of
the Schist-Metagraywacke Complex (CEG). In the studied area,
these rocks exhibit medium to high degrees of metamorphism,
with assemblages containing biotite, sillimanite, staurolite,
cordierite, feldspars, and muscovite (Martin-Izard et al. 1992).
According to these authors, all these rocks have undergone two
main phases of Hercynian deformation.
The Caada pegmatite strikes E-W and dips 60 N. It has a
maximum width of 10 m in outcrop and a length of ~70 m. The
pegmatite displays clear deformation effects, e.g. undulatory
extinction, subgrains in plagioclase and magniotriplite, bending
and kinking in micas, foliated textures where micas wrap around
garnet crystals, and granoblastic textures in some phosphates. It
was mined for feldspar, and the open pit is located mainly in the
gabbro-hosted part of the pegmatite. In this open pit, the pegmatite
is aparently fairly homogeneous and unzoned, except for the
phosphate phases. The pegmatite consists of quartz, plagioclase,
K-feldspar, muscovite, and Fe-Mn-(Li-Mg) phosphates (Table

112

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

1), with minor tourmaline, garnet, ferrocolumbite, cassiterite,

and pyrite. Uraninite, Fe-Mn carbonates, corundum, ilmenite,
and zircon occur as accessories.
In the contact zone of the pegmatite, the phosphates are
dark in color (mainly brown and black), and they belong to
the border zone association [with ferrisicklerite, magniotriplite,
johnsomervilleite, manganoan fluorapatite, and xenotime-(Y) as
the main phosphates]. They appear as decimeter-sized masses,
together with K-feldspar, schorl, biotite, muscovite, and garnet. In
the inner zone of the pegmatitic body, another association appears.
Samples of this association are masses, up to a meter in size, of
light gray to gray triphylite and sarcopside, which appear together
with plagioclase and muscovite. Finally, the third association
appears in a transition zone (with ferrisicklerite and graftonite
as main phosphates), between the border and the inner zones.
All the sampling of Fe-Mn phosphate was done in the part
of the pegmatite intruded into the gabbro because no phosphate
phases have been observed in the outcrop of the pegmatite where
it intrudes into the leucogranite. Although it is not possible to
observe the transition from one association to another, as they
do not crop out together, a knowledge of the position of the
three associations in the pegmatitic body (contact or inner
zone) permitted us to study the evolution of the phosphates
through the pegmatite. In this regard, it is noteworthy that the
chemical compositions of the phosphates change dramatically
from one association to another, mainly in their Mg contents.
This difference is evident not only in the phosphate phases, but
also in most of the other phases (e.g., tourmaline and mica).
Moreover, some of the minerals only occur together with some
of the phosphates: ferrocolumbite, cassiterite, and uraninite
are exclusively associated with triphylite, whereas garnet
and ilmenite only appear together with magniotriplite and
johnsomervilleite (Tables 2 and 3).

DATA COLLECTION AND ANALYTICAL PROCEDURE

The studied phosphate samples were collected mainly from the walls of
the open pit. In addition, a few samples were collected from the dumps, as their
similarity with the in situ samples let us utilize them with a high degree of
reliability. Moreover, we have relied extensively on the information provided by
A. Martn-Izard, who did his thesis on the igneous rocks of this area, during the
mining of the pegmatitic body.
Mineral identification was carried out by a combination of petrographic, powder
X-ray diffraction, and electron-microprobe techniques. Chemical analyses were
performed at the Universit Paul Sabatier (Toulouse, France), with a Camebax
SX 50 electron microprobe. The operating conditions were: accelerating voltage
of 15 kV and a beam current of 20 nA for all elements, with a beam spot size
around 10 micrometers. The standards used for the phosphates were: fluorite for
F; apatite for P; albite for Na; andradite for Fe, Ca, and Si; graftonite for Mn; titanite for Ti; olivine for Mg; and ZnS for Zn. For the other minerals, the standards
were: LiNbO3 for Nb; LiTaO3 for Ta; titanite for Ti; SnO2 for Sn; W metal for W;
hematite for Fe; graftonite for Mn; albite for Na; orthoclase for K; corundum for
Al; wollastonite for Ca; MgO for Mg, and sphalerite for Zn. Finally, for rare-earth
elements in xenotime-Y and uraninite, the standards used are given in Jarosewich
and Boatner (1991). The analytical data were reduced and corrected by the PAP
method (Pouchou and Pichoir 1984).

PETROGRAPHY AND MINERAL CHEMISTRY

Border-zone association, with ferrisicklerite, magniotriplite, and johnsomervilleite
Ferrisicklerite is the most abundant phosphate in this association. It appears in close relation with the primary phosphates

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

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

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

jhsm, mgtr, grft, xnt

Mn-apt, allu, stnk,
crd,coll,lcp,whit,grn,bio,tour

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

granobl. and interlayered

textures, an- to euhedral h.

fine
to coarse

>0.65

fsck-xntm
mgtr

Xenotime-Y

sub- to euhedral habit

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

skeletal, anhedral habit

very fine to medium

0.540.79

fsck, stnk

Stankite

anhedral habit

very fine to fine

0.690.78

fsck, grft, jhsm

Silicates
Garnet

sub- to euhedral habit

fine to
medium

0.900.98

bio, tour, musc,

mgtr, jhsm, fsck, grft

Muscovite

subhedral habit

fine to coarse

0.63

cor, bio, grn, fsck

Biotite

subhedral habit

fine to medium

0.68

grnt, tour, musc, mgtr, fsck

Tourmaline

subhedral habit

fine to coarse

0.59

grnt, musc, bio, mgtr, fsck, jhsm

Oxides
Corundum
subhedral habit

rounded to irregular,

very fine

musc, bio

granoblastic and
graphic textures,

fine to
coarse

0.720.90

grft, allu, hur, stnk,whit,rckb,mtbr

ABP2,eosp,grm,lcp,crd,qz,tour,bio

Graftonite

granoblastic and graphic textures

an- to subhedral habit

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

sub- to euhedral habit

very fine-

Secondary phosphates
Alluaudite

skeletal, anhedral habit

very fine to medium

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

qz, tour, grft, fsck

fsck and grft

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 (see below), it is typical of the border zone where it appears

as subrounded to coarse prismatic crystals up to 4 cm in length
(Table 2). Textural relationships between manganoan fluorapatite
and ferrisicklerite vary from striped intergrowths to ellipsoidal
apatite grains within the ferrisicklerite (Fig. 3c). In the border

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

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

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

srcp wolf, barb, hur, whit

viv, allu, fsck, mtbr, grm, musc

Graftonite

granoblastic texture

very fine to fine

0.98

fsck srcp

Wolfeite

anhedral habit

very fine

0.920.96

trph srcp

Montebrasite

subhedral habit, twinning

very fine to fine

trph srcp, eosp, fsck, allu,

Exsolution phosphates
Sarcopside
lamellar, twinned

fine to medium

0.960.97

trph wolf, fsck srcp, musc

Secondary phosphates
Ferrisicklerite
granoblastic texture

fine to medium

0.93-0.96

trph, srcp, allu, stnk, F-apt

Alluaudite

skeletal anhedral habit

very fine to fine

0.880.97

trph srcp, barb

Barbosalite

anhedral habit, cellular texture

very fine to fine

0.940.99

trph, hur, whit, allu

Hureaulite

very fine
to fine
very fine
to fine
very fine
to fine
very fine to fine

0.700.99

Stankite

an- to euhedral habit

cellular texture
sub- to
anhedral habit
sub- to
anhedral habit
anhedral habit

0.930.97

trph, barb, whit, redd

rckb, lpcb, jahn, mtr
trph, arrj, barb, hur
ura, Fe-Mn carb, frf,pyr
trph, sml, barb, hur
ura, Fe-Mn carb, frf, pyr
fsck srcp

Gormanite-souzalite

anhedral habit

very fine to fine

0.910.94

trph, srcp

Silicates
Plagioclase
Muscovite

subhedral
tabular habit

fine to mdium
fine to coarse

0.86

trphsrcp
trphsrcp

Biotite

subhedral habit

very fine to fine

musc, barb, allu, sml, arrj

Tourmaline

sub- to euhedral habit

fine

0.86

trphsrcp

Oxides
Cassiterite

subhedral habit

fine to medium

trphsrcp, musc, col

Ferrocolumbite

tabular habit

fine to medium

trphsrcp, musc, cass

Uraninite

rounded habit

very fine

Primary phosphates
Triphylite

ABP1
Arrojadite

0.970.98
0.88

trph, arrj, sml,

barb, hur, Fe-Mn carb
Notes: The following abreviations have been used: triphylite = trph; sarcopside = srcp; graftonite = grft; wolfeite = wolf; ferrisicklerite = fsck; alluaudite = allu;
montebrasite = mtbr; barbosalite = barb; huraulite = hur; arrojadite = arrj; stankite = stnk; gormanite-souzalite = grm; lpcb = lipscombite; F-apt = fluorapatite;
eosp = eosphorite; whiteite = whit; vivianite = viv; rckb = rockbridgeite; jahn = jahnsite; mtr = mitridatite; frf = fairfieldite; redd = reddingite; plagioclase = plg;
muscovite = musc; biotite = bio; tourmaline = tour; cassiterite = cass; columbite-tantalite = col; uraninite = ura; quartz = qz; Fe-Mn carbonates = Fe-Mn carb; pyr
= pyrite. * grain size: very fine = < 1 mm; fine = 1 to 5 mm; medium = 5 mm to 2.5 cm; coarse = > 2.5 cm.

F content and mineral association has not been detected.

Euhedral fine-grained crystals of xenotime-(Y) are common
in the border zone (Fig. 3c). This mineral is characteristic of
peraluminous leucogranites (Bea 1996), and although it seems
to be included mainly within biotite (Bea 1996), xenotime-(Y) is
invariably associated here with the above-described intergrowths
of ferrisicklerite and manganoan fluorapatite. Xenotime-(Y), with
an average Y2O3 content of ~43.3 wt%, exhibits moderate enrichment in Yb2O3 (avg. ~2.7 wt%), Dy2O3 (6.4 wt%), and Gd2O3
(up to 4.3 wt%; see Table 5).
Petrographic relationships indicate that graftonite is later than
ferrisicklerite in the border zone. A similar sequence involving
secondary graftonite has been pointed out in other phosphate
associations (Fransolet 1977; Corbell and Melgarejo 1990).
The CaO and MgO contents of graftonite from the border zone
are the highest in this pegmatite body. The average CaO contents are ~10.5 wt%, whereas the Fe/(Fe + Mg) values are ~0.85

(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

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

115

FIGURE 2. Plot of the variation in the contents in Mg, Fe total (as

Fe2+), and Mn for the main phosphates of the three associations.

alluaudite. As the other phases of this association, alluaudites

from the border zone are the richest in Mg (Table 6).
Stankite replaces ferrisicklerite, johnsomervilleite, and
graftonite. In the first case, stankite occurs along the grain
boundaries and at triple junctions associated with granoblastic
ferrisicklerite (Fig. 3d). Like the other phases from the border
zone, stankite is relatively rich in Mg (Table 4, Fig. 2a).
Silicates. Quartz, K-feldspar, plagioclase, muscovite, biotite,
tourmaline, and garnet are the main silicates in the border zone.
Biotite and tourmaline are more abundant in the border zone than
in the two other associations. The mean MgO content of biotite
is ~6.5 wt% (Table 7). It appears as a primary phase together
with magniotriplite and ferrisicklerite. Muscovite includes tiny
rounded to irregular subhedral corundum crystals (<50 m)
coexisting with small plates of biotite (Fig. 3e).
Tourmaline corresponds to the schorl-rich member with 40%
of the olenite component, but shows higher Mg contents in relation to tourmaline from the other associations, being characterized by a decrease in Fe (Table 8).
Garnet usually appears as fine- to medium-grained, euhedral
to subhedral, brown crystals (Fig. 3d), closely associated with
biotite, muscovite, tourmaline, magniotriplite, johnsomervilleite, ferrisicklerite, and graftonite. Its chemical composition
(Alm59Sps38Prp3) corresponds to an almandine with a substantial

spessartine content. In places, garnet crystals are fractured and

replaced by white mica and chlorite. Moreover, micas wrap
around some garnet crystals, producing foliated textures.
Transition zone association, with ferrisicklerite and
graftonite
Primary phosphates. Ferrisicklerite is an ubiquitous phosphate in the transition zone, where it commonly appears as a
primary phase. Graphic and skeletal intergrowths of subhedral
and subrounded crystals of graftonite + ferrisicklerite can be
observed, which have undergone partial resorption by quartz,
biotite, and/or tourmaline (Fig. 3f). Replacements of granoblastic ferrisicklerite by alluaudite and stankite are common. Like
other minerals present in the transition zone, ferrisicklerite in
this assemblage contains less Mg than in the border zone, with
an average MgO content of ~3.3 wt% (Table 9, Fig. 2b).
Graftonite is the other main primary phosphate of the transition zone, with average MgO and CaO contents of 0.9 and 8.4
wt%, respectively (Table 9, Fig. 2b), which are lower than in the
border zone. Minor manganoan fluorapatite (average MnO ~4.6
wt%, Table 9), xenotime-(Y), and montebrasite are additional
primary phosphates of the transition zone. In this association,
xenotime-(Y) and manganoan fluorapatite exhibit the same
textures as in the border zone.

116

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

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

Secondary phosphates. Besides alluaudite and stankite, hureaulite, eosphorite,

gormanite-souzalite, leucophosphite, crandallite, rockbridgeite, and whiteite are present (Table 1). Moreover, a phosphate with a similar chemical composition to that of
wilhelmvierlingite (ABP2), is found only in this transiton zone.
Silicates. In addition to quartz, biotite, and tourmaline, appreciable amounts of
plagioclase and muscovite appear in the transition zone. The average Fe/(Fe + Mg)
ratio of biotite is 0.86 (Table 7). Although biotite is not commonly associated with (Li)Fe-Mn-Mg phosphates, a few such occurrences have been described previously (e.g.,
Chapman 1943; Wolfe and Heinrich 1947; London et al. 1999). Tourmaline from the
transition zone is rich in schorl with ~40 mol% of the foitite component. The average
Fe/(Fe + Mg) and Na/(Na + Ca) ratios are 0.74 and 0.98, respectively (Table 8).
Inner zone association with triphylite and sarcopside
Primary phosphates. Triphylite occurs exclusively in the inner zone of the Caada
pegmatite, where it is by far the most abundant phosphate. It appears as decimeter-sized
blocks (up to ~1 m) with a grayish color in hand specimen. In thin section, triphylite
exhibits abundant sarcopside lamellae (Fig. 4a; see page 12). The replacement of
triphylite by ferrisicklerite is not rare, but it is more typically replaced by alluaudite.
Portions of triphylite may be partially or totally altered to barbosalite, which usually
shows a cellular texture intergrown with alluaudite or huraulite and whiteite (Fig. 4b).
In these alteration zones, arrojadite is present, together with another phosphate phase
(ABP1) having a composition similar to that of samuelsonite. Moreover, anhedral,
fine-grained Fe-Mn carbonates, and fine-grained, rounded crystals of uraninite, are
also common. Microfractures in triphylite are usually lined by huraulite, whiteite,

TABLE 5.
P2O5
CaO
Y2O3
La2O3
Ce2O3
Nd2O3
Sm2O3
Gd2O3
Tb2O3
Dy2O3
Ho2O3
Er2O3
Tm2O3
Yb2O3
Total

Representative chemical composition* of xenotime-Y

35.31
0.31
43.27
0.00
0.00
0.20
0.77
4.30
0.78
6.38
1.07
3.15
0.28
2.69
98.51

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.

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

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

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

TABLE 6. Chemical compositions* of alluaudite from the three associations

Border Zone
N
P2O5
Al2O3
FeO
MnO
MgO
ZnO
CaO
K2O
Na2O
Total

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.

lipscombite, Mn-(Fe) oxides, and (rarely) acicular crystals of

rockbridgeite (Fig. 4c).
Representative microprobe analyses of triphylite are given in
Table 10. It has an average Fe/(Fe + Mn) ratio of 0.81, and a low
Mg content of ~0.23 Mg atoms per formula unit (apfu), with an
Fe/(Fe + Mg) ratio ranging from 0.91 to 0.95 (Fig. 2c).
Graftonite is a minor constituent and exhibits a granoblastic
texture (Figs. 4d and 4e). It is closely associated with ferrisicklerite, never being observed in contact with triphylite. Its Fe/(Fe
+ Mn) ratio of ~0.61 (Table 10) corresponds to an intermediate
member of the beusite-graftonite series. The Mg and Ca contents
in graftonite from the inner zone are the lowest of the three associations, with a mean Fe/(Fe + Mg) value of 0.98 and with
6.97 wt% CaO (Table 10, Fig. 2c).
Wolfeite is a rather minor constituent of the inner zone,
occurring as fine, anhedral grains in association with coarse,
anhedral triphylite (Fig. 4b), from which it is difficult to distinguish under the microscope. Due to its scarcity, only nine
point analyses have been obtained on wolfeite. These analyses
(Table 10) reveal low concentrations of MgO (<2.8 wt%), and
a mean Fe/(Fe + Mg) value of 0.94. The average Fe/(Fe + Mn)
ratio of ~0.78 corresponds to an intermediate member of the

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.

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

TABLE 7. Chemical compositions* of muscovite and biotite

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

Chemical compositions* of tourmaline from the three associations

Border Z.
5
36.32
0.63
33.06
0.01
10.10
0.15
3.92
0.06
2.03
0.04
86.32

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

Chemical compositions* of the main phosphates from the

transition zone association
fsck
28
44.72
0.01
36.75
0.00
10.33
3.29
0.03
0.24
0.22
0.13
n.a.
n.a.
95.73

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

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

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.

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

121

FIGURE 4. Photomicrographs of some textures of the inner zone

association: (a) sarcopside (srcp) lamellae inside triphylite (trph).
Crossed-polarized light; (b) anhedral crystal of wolfeite (wolf)
together with triphylite (trph), which is partially replaced by a cellular
intergrowth of barbosalite (barb) and whiteite (whit) + hureaulite (hur).
Plane-polarized light; (c) fracture filling in triphylite (trph), by hureaulite
(hur), whiteite (whit), and lipscombite (lpcb). Crossed-polarized light;
(d) rounded crystals of ferrisicklerite (fsck) mantled by sarcopside (srcp),
and together with granoblastic graftonite (grft). Plane-polarized light;
and, (e) granoblastic graftonite (grft) and ferrisicklerite (fsck), which
is mantled by sarcopside (srcp), that also appears as lamellae inside
ferrisicklerite (fsck) in the upper left corner of the photograph. Plane
polarized light. (Scale for a, b, c, and e = 1.8 2.6 mm. Scale for d =
0.4 0.6 mm).

similar to that of the replaced triphylite (Table 10, Fig. 2c).

Alluaudite is an ubiquitous secondary phosphate. It mainly
replaces triphylite and locally ferrisicklerite. In the first case, the
replacement gives rise to cellular intergrowths of alluaudite and

barbosalite and/or spots of fine-grained subhedral alluaudite. In

both cases, alluaudite is strongly pleochroic, showing deep-green
to brownish absorption colors. Ferrisicklerite may exhibit slightly
pleochroic patches of yellow to light-brownish alluaudite as a
result of replacement processes. Similar to other phosphates in
the inner zone, the MgO contents of alluaudite are low, ranging
from 0.87 to 1.15 wt% (Table 6, Fig. 2c).
Arrojadite and ABP1 are found in the alteration zones of
triphylite,. Arrojadite exhibits a sub- to anhedral shape and it

122

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

is very fine-grained, with a pleochroism from colorless to pale

yellow. The Mg contents are higher than those of ABP1, with a
Fe/(Fe + Mg) ratio of 0.88 (Table 10, Fig. 2a). ABP1 appears as
sub- to anhedral very fine-grained crystals, black to dark green
in color. It contains low Mg with an Fe/(Fe + Mg) ratio of 0.98
(Table 10, Fig. 2c).
Other secondary phosphates in the inner zone are fluorapatite,
eosphorite, jahnsite, gormanite-souzalite, mitridatite, fairfieldite,
reddingite, whiteite, and vivianite (Tables 1 and 3).
Silicates. Plagioclase is albitized, showing a chess-board
texture in places. Muscovite appears as tabular crystals, commonly showing foliated textures with chevron domains, undulatory extinction, and kinking. The amounts of Fe + Mn + Mg and
F are very low (<0.4 apfu and <0.10 apfu, respectively), and Li
presumably is present only in trace quantities taking into account
the total cation occupancy of the Y site (Table 7).
Tourmaline is a schorl-rich variety with Fe and Mg contents
of ~2.15 and 0.34 apfu, respectively (Table 8), with appreciable
foitite component (~40 mol%). Under the microscope, tourmaline
appears as euhedral to subhedral fine-grained crystals showing an
intense pleochroism from deep- to pale-blue or colorless.
Oxides. Cassiterite appears as subhedral crystals (<1 cm)
that usually display geniculate twinning. It usually exhibits concentric color zoning, with alternating pale (pleochroism ranging
from light-brown to beige) and dark bands (dark-brown to reddish-brown pleochroism), similar to other cassiterite crystals
described in this region (Roda et at. 1999). Its SnO2 content
is ~99.5 wt%, with Nb2O5 and Ta2O5 values always under 0.5
wt% (Table 11).
Ferrocolumbite forms tabular small crystals (<1 cm in length),
always in close association with cassiterite. Concentrations of
Nb2O5 are much higher than those of Ta2O5 (>60 vs. <13.5 wt%,
respectively). The FeO values are much higher than those of
MnO (>15.5 vs. <3.0 wt%) (Table 11).
Uraninite exhibits rounded shapes, with a very fine grain size
(<1 mm). It usually appears in close relation with arrojadite,
ABP1, and Fe-Mn carbonates, in areas where triphylite is altered
to barbosalite, huraulite, and whiteite. The UO2 contents are
high (~92.5 wt%), whereas the ThO2 values are very low, always
under 0.5 wt% (Table 11).

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-

tion and distribution; (2) development of graphic and skeletal

textures in the border and transition zones that suggest rapid
disequilibrium-induced growth due to relatively high degrees of
undercooling; (3) the Fe/(Fe + Mg) ratio for mafic phosphates and
silicates that increases from the border to the inner zone; and (4)
the occurence of minerals relatively rich in Mg, Fe, and/or Ca in
the border zone due to possible contamination of the pegmatite
system by the mafic host rock.
Paragenetic and compositional relationships
The association of the inner zone shows characteristics typical
of an evolved pegmatitic facies, such as the abundance of triphylite, muscovite, cassiterite, and ferrocolumbite, and with very
low proportions of mafic components (Fig. 5). In contrast, the
association of the border zone is characterized by minor amounts
of Li-bearing minerals, a relative abundance of garnet, biotite,
and tourmaline, and the occurrence of Mg-rich phosphates. Thus,
the association of the border zone is less-evolved than the others
(Fig. 5). The association of the transition zone shares features in
common with the two other assemblages and is thus a transitional
facies. Alteration sequences deduced from the petrography of the
three phosphate associations are proposed in Figure 6.
The Fe/(Fe + Mn) ratios of ferrisicklerite and graftonite are
frequently used to establish the degree of evolution in pegmatites. Here, these ratios are not suitable to establish the degree
of evolution attained for the three associations because the Mn
contents remain constant throughout. However, the Fe/(Fe + Mg)
ratio seems to be more suitable for this purpose. Overall, the association of the inner zone appear to be the most evolved of the
three as the Fe/(Fe + Mg) ratios for inner-zone ferrisicklerite,
graftonite, alluaudite, stankite, tourmaline, and biotite are the
highest (Tables 4, 6, 7, 8, 9, and 10). In the case of alluaudite,
we must take into account the existence of appreciable chemical variability within the same association. However, its Fe/(Fe
+ Mg) ratio ranges from 0.54 in the border zone to 0.94 in the
inner zone, with intermediate values of 0.85 to 0.90 in the transition zone (Table 6). The presence of Mn-bearing almandine in
the border zone also would be evidence for a lower degree of
evolution of this association, as is its restriction to the margins of
the pegmatitic body, according to ern and Hawthorne (1982)
and Whitworth (1992). Moreover, the occurrence of the Fe-Mg
member of the johnsomervilleite-fillowite series in this border
zone would be indicative of a poorly evolved pegmatitic facies
(e.g., Corbell and Melgarejo 1990; ern et al. 1998).
Graphic and skeletal intergrowths between silicates and phosphates (Fig. 3f) suggest concurrent crystallization of these phases.
Such intergrowths, as well as the assemblage of biotite, garnet,
and tourmaline with Fe-Mn-Mg phosphates in the border zone,
are of special interest because they appear to be rare (London et
al. 1999; Alfonso and Melgarejo 2000). According to London et
al. (1999), if mafic silicates and phosphates do appear in the same
pegmatite body, their crystallization generally is not simultaneous, but sequential. In the Caada pegmatite, however, petrographic observations of the border zone, as well as the graphic
intergrowths of biotite and tourmaline with ferrisicklerite and
graftonite in the transition zone, suggest overlaping or simultaneous crystallization of Fe-Mg silicates and phosphates.
The formation of such a paragenesis indicates the availability

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE

FIGURE 5. Idealized scheme of the phosphate associations distribution

in the Caada pegmatite.

of ferromagnesian components in the melt. As the solubility of

Fe and Mg in peraluminous granitic melts is low (Puziewicz
and Johannes 1988, 1990), an appreciable amount of Fe and Mg
may have been introduced into the pegmatite system via aqueous
fluids that circulated through the host mafic rock. Circulation may
have been driven by temperature and chemical gradients produced during the emplacement of the pegmatite, which removed
Mg, Fe, and Ca and added Na and K to the mafic rock.
The isotopic signatures of border zones and fluid inclusion
data from other localitities suggest that initially, pegmatites are
open to mass transfer from wall rocks (Taylor et al. 1979; Taylor
and Friedrichsen 1983; Thomas and Spooner 1988). In the early
stages of crystallization, a pegmatite rich in fluxing components,
such as B and P, is open to assimilation of Fe-Mg components
from the wall rocks (London 1992). A mineralogical indicator
of such an early assimilation in the Caada pegmatite is represented by the occurrence of Mg-rich phosphates and silicates in
the border zone (Tables 1, 2, and 3). Biotites from rare-element
pegmatites are typically Mg-poor (Foster 1960; ern and Burt
1984). Hence, the decrease of the Fe/(Fe + Mg) ratio for biotites
of the border zone also could be indicative of the assimilation
of material from surrounding rocks into pegmatite system; the
mafic components having been leached from the gabbro by the
fluids. Thus, the border zone with abundant Mg-rich phosphates,

123

FIGURE 6. Diagram showing alteration sequences of phosphate

minerals from the three associations.

tourmaline, and biotite could represent the site of assimilative

mixing within the pegmatite system.
Although desilicification of the pegmatitic fluid by highly
silica-undersaturated wall rocks has been invoked to explain
the origin of corundum (Rossovsky and Konovalenko 1977), the
presence of anhedral, fine-grained corundum crystals, coexisting
with small biotite crystals, within muscovite in the border zone,
together with absence of K-feldspar or andalusite, suggests a
reaction such as:
muscovite + Mg-Fe-bearing aqueous fluids = biotite +
corundum + SiO2
According to this reaction, the small plates of biotite
associated with corundum (Fig. 3e) would have a secondary
origin, whereas muscovite exhibits the textural and chemical
features of a primary phase, following the criteria proposed
by Miller et al. (1981). This secondary biotite, associated with
corundum and primary muscovite, has not been observed in the
two other associations.
The pegmatitic association of corundum suggests the
important role of the fluids (Clarke 1981), as it is indicated
by other minerals such as biotite. The formation of biotite and
tourmaline in the border zone suggests a relatively high H2O

124

RODA ET AL.: PHOSPHATE MINERAL ASSOCIATIONS IN THE CAADA PEGMATITE:

content in the melt. The crystallization sequence for biotite

depends on the H2O content, with biotite crystallizing out earlier
at higher H2O contents (Maale and Wyllie 1975).
Behavior and abundance of P
Phosphorus has a marked influence on the evolution of silicate
melts. It significantly alters the chemical and physical properties
of the magmas, such as melt viscosity, solidus temperatures,
geochemical behavior of the REE, U, Th, Sr, and other trace
elements, redox equilibria of Fe, etc. (Bea et al. 1992; Dingwell
et al. 1993; Gwinn and Hess 1993; London et al. 1993; Toplis et
al. 1994; Mysen et al. 1999). Phosphorus behaves as a high-fieldstrength incompatible element, but as magmatic crystallization
proceeds, the melts may eventually become saturated with apatite
depending on the Ca/P ratio in melt.
Presumably, apatite is the main P source for peraluminous
magmas derived from the melting of metapelites. Apatite appears to be more soluble in peraluminous melts (ASI>1) than in
metaluminous melts (Montel et al. 1988; Bea et al. 1992; Mysen
et al. 1997). Wolf and London (1994) showed experimentally
that the solubilities of apatite in a haplogranitic melt increase
linearly with increasing Al2O3 saturation. The solubility of other
phosphates such as xenotime and monazite is much lower (Montel 1986; Wolf and London 1995). Only in those cases where
REE concentrations equal that of P, could monazite or xenotime,
instead of apatite, be the source of REE and P (Wolf and London
1995). The high solubility of apatite in peraluminous granitic
melts is attributed to a low activity of Ca in the melt, as well as
to the formation of aluminophosphate complexes. In the case
of the Caada pegmatite, the peraluminous composition of the
host leucogranite, with ASI ~1.35 (average normative corundum
and apatite are 3.7% and 0.5%, respectively), low CaO contents
(<0.45 wt%), and low REE concentrations, suggest that the incorporation of P in the melt is mainly due to the high solubility of apatite at the source. On the other hand, London (1997)
established an ASI value of 1.3 for the dissolution of apatite
and the precipitation of xenotime and monazite at the source.
Although Wolf and London (1995) observed that the solubility
of phosphates such as xenotime was not appreciably enhanced
in peraluminous melts, the occurrence of xenotime-(Y) in close
association with apatite and ferrisicklerite in the border and in
the transition zones suggests that both apatite and xenotime could
have been dissolved at the source, and could have been prevented
from precipitating until the pegmatite-crystallization stage. The
crystallization of plagioclase in the parental granite should cause
a decrease in the Ca/P ratio in the melt. Hence, apatite precipitation would be limited and P would behave as an incompatible
element, thus increasing in abundance with fractionation. According to Bea et al. (1992), in perphosphorous melts (those with
more P2O5 than CaO to form normative apatite), an excess of
P2O5 in late differentiates becomes greater from the point where
apatite no longer precipitates, that is, where P first behaves as an
incompatible element. This P, progressively concentrated in the
residual melt, would be discharged during the pegmatite crystallization by the formation of phosphates and/or through tetrahedral
substitution within the lattice of the feldspars. In the first case, if
the pegmatitic melt is Li-rich, phosphate minerals such as triphylite-lithiophilite could be found, which are the first Li-minerals to

crystallize (Varlamoff 19581959). In the Caada pegmatite, at

the beginning of pegmatitic crystallization, and together with the
formation of biotite, garnet, and tourmaline, primary phosphates
such as xenotime-(Y), manganoan fluorapatite, ferrisicklerite,
magniotriplite, and johnsomervilleite crystallized. According to
Bea et al. (1992), apatite would be the first-crystallized phosphate. However, in the present case, there is no clear evidence of
early apatite crystallization, partly as a result of the deformation
and recrystallization processes developed during the Hercynian
deformation and metamorphism, giving undulatory extinction,
subgrains in magniotriplite, and granoblastic textures in some
phosphates. Only xenotime-(Y) seems to have formed earlier than
the manganoan fluorapatite and ferrisicklerite associated with it,
as expected, taking into account the lower solubility of xenotime
in melt relative to apatite. Although the early crystallization of
plagioclase from the melt could have limited the precipitation of
apatite, the influence of the host gabbro also must be considered
as it appears to have provided Ca to the pegmatitic system. This
influence could also account for the progressive disappearance of
apatite and the depletion of Ca from the outermost border zone
to the inner zone, mainly evidenced in the graftonite.
Despite the low P2O5 contents reported for the leucogranite parental to the Caada pegmatite (avg. = 0.21 wt% P2O5,
Martn-Izard 1979), fractionation to P-rich compositions due to
the instability of apatite would account for the formation of the
different phosphate associations found in the pegmatite. Unfortunately, the lack of data on the P contents of alkali feldspars
hinders the assessment of the P budget in the Caada pegmatite
on the basis of the distribution of P between alkali feldspar and
melt, and the ASI value (London et al. 1999). However, the occurrence of Fe-Mg-Mn phosphates along with Fe-Mg silicates
suggest that the P content of the melt may have been on the order
of 1.3 to 2.4 wt% P2O5 following the considerations of London
et al. (1999). Anyway, additional work is necessary on the mafic
silicate-phosphate associations in the Caada pegmatite to assess
the budget of P in the melt.

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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