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Titanian ixiolite - Niobian rutile intergrowths from the

Borborema Pegmatitic Province, northeastern Brazil

Article  in  The Canadian Mineralogist · December 2007

DOI: 10.3749/canmin.45.6.1367

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 1367

The Canadian Mineralogist

Vol. 45, pp. 1367-1387 (2007)
DOI : 10.3749/canmin.45.6.1367

TITANIAN IXIOLITE – NIOBIAN RUTILE INTERGROWTHS

FROM THE BORBOREMA PEGMATITIC PROVINCE, NORTHEASTERN BRAZIL

Hartmut BEURLEN§
Programa de PG em Geociências, Universidade Federal de Pernambuco, Rua Acadêmico Hélio Ramos s.n.,
50740–530 Recife, Pernambuco, Brazil

Sandra Brito BARRETO

Deptamento de Geologia, Universidade Federal de Pernambuco, Rua Acadêmico Hélio Ramos s.n.,
50740–530, Recife, Pernambuco, Brazil

Dailto SILVA
Instituto de Geociências, IGE–UNICAMP, Cidade Universitária Zeferino Vaz, Distrito Barão Geraldo,
13083–970 Campinas, São Paulo State, Brazil

Richard WIRTH
GeoForschungsZentrum Potsdam, Telegrafenberg B 120, D–14473 Potsdam, Germany

Patrick OLIVIER
Curso Geologia, Universidade Federal de Pernambuco, Rua Acadêmico Hélio Ramos s.n.,
50740–530, Recife, Pernambuco, Brazil

Abstract

Intergrowths of orthorhombic and tetragonal Nb–Ta–Ti–(Sn) oxides were at first recognized by conventional X-ray diffraction
and electron-microprobe analyses in six pegmatite occurrences of the Borborema Pegmatitic Province in northeastern Brazil.
In three of these cases, electron-diffraction patterns (HRTEM) on chips 0.15 mm thick obtained by focused ion-beam (FIB)
sampling were necessary to confirm the preliminary identification of titanian ixiolite. Electron-microprobe analyses reveal very
variable bulk-compositions and extents of compositional gaps between the coexisting tetragonal and orthorhombic phases in the
Nb,Ta – Ti,Sn – Fe,Mn triangular plot. This behavior is difficult to explain as a result of a simple solvus along a pseudobinary
section between rutile and tapiolite – columbite – ixiolite – wodginite. In two of six cases, the data obtained plot exactly within
the compositional gaps observed between these phases in other pegmatitic provinces. This apparent violation of the gap is due
to abnormally high Ti-contents in ixiolite and high levels of Ta + Nb (up to 55 wt.% Nb + Ta oxides) observed in the tetragonal
phase. Therefore, in the cases studied, the observed trends and gaps seem to be the result of disequilibrium (or incomplete equi-
librium) between the coexisting phases, despite the exsolution-like, cuneiform to vermicular intergrowths observed in three of
the occurrences studied. Compositional growth-zoning observed in the other cases agrees with the hypothesis of disequilibrium.
In five of the six cases, a partition of Ta and Fe in favor of the tetragonal phase and of Nb and Mn in the coexisting orthorhombic
phase is observed; it agrees with the behavior of similar intergrowths elsewhere. The sixth case is noteworthy because of the
higher Ta:Nb ratio in the ixiolite in comparison with the coexisting niobian rutile. This enrichment of Nb and Fe from core to
rim represents an anomalous pattern of fractionation behavior.

Keywords: titanian ixiolite, niobian rutile, intergrowths, exsolution, compositional variations, rare-element-enriched granitic
pegmatites, Borborema Province, northeastern Brazil.

§ E-mail address: beurlen@ufpe.br

1368 the canadian mineralogist

Sommaire

Nous avons d’abord documenté la présence d’oxydes orthorhombique et tétragonal de Nb–Ta–Ti–(Sn) par approche
conventionnelle avec diffraction X et analyses par microsonde électronique dans six exemples de pegmatite granitiques de la
province pegmatitique de Borborema, dans le nord-est du Brésil. Dans trois des cas, nous avons de plus eu recours à la diffrac-
tion d’électrons en microscopie électronique par transmission; nous avons analysé des pellicules d’une épaisseur de 0.15 mm,
obtenues par échantillonage avec un faisceau d’ions focalisé (FIB) afin de confirmer notre identification préliminaire de l’ixiolite
titanifère. Les analyses à la microsonde électronique révèlent des compositions globales et des étendues des lacunes de miscibilité
très variables entre les phases tétragonale et orthorhombique coexistantes dans un diagramme triangulaire Nb,Ta – Ti,Sn – Fe,Mn.
Ce comportement est très difficile à expliquer en termes d’un simple solvus dans une section pseudobinaire entre rutile et tapi-
olite – columbite – ixiolite – wodginite. Dans deux des six cas, les points apparaissent à l’intérieur des lacunes de miscibilité
observées entre ces phases dans d’autres provinces pegmatitiques. Cette violation de la lacune de miscibilité serait due à une
teneur en Ti anormalement élevée dans l’ixiolite et une teneur anormalent élevée en Ta + Nb (jusqu’à 55% en oxydes de Nb +
Ta) dans la phase tétragonale. A notre avis, dans les cas étudiés ici, les tracés et les lacunes semblent résulter d’un déséquilibre
(ou d’un équilibre incomplet) parmi les phases coexistantes, malgré la forme cunéiforme à vermiculaire des intercroissances
attribuables à l’exsolution dans trois des cas étudiés. La zonation compositionnelle pendant la croissance observée dans les autres
cas concorde avec l’hypothèse d’un déséquilibre. Dans cinq des six cas, nous trouvons une répartition de Ta et Fe en faveur de
la phase tétragonale, et du Nb et Mn dans la phase orthorhombique coexistante. Ce schéma concorde avec ce que l’on trouve
dans des intercroissances semblables ailleurs. Le sixième cas est anomale à cause du rapport Ta:Nb plus élevé dans l’ixiolite en
comparaison avec le rutile niobifère coexistant. Cet enrichissement du Nb et du Fe du coeur des grains vers la bordure manifeste
un tracé anomale du fractionnement dans ce cas.

(Tracduit par la Rédaction)

Mots-clés: ixiolite titanifère, rutile niobifère, intercroissance, exsolution, variations en composition, pegmatites granitiques
enrichies en éléments rares, province pegmatitique de Borborema, Brésil.

Introduction Geological Setting

Niobium- and Ta-bearing rutile (formerly known
as “ilmenorutile” and “strüverite”, respectively) were
mentioned by Rolff (1946) as accessory minerals in
the granitic pegmatites of the Borborema Pegmatitic
Province (BPP), northeastern Brazil, without further
information. Adusumili (1978) reported a chemical
composition of the first confirmed occurrence of niobian
rutile from the Lira pegmatite, Santa Luzia, State of
Paraíba, in the BPP, and another one of Ta-bearing rutile
from the Icozinho pegmatite, Icó, State of Ceará, beyond
the area of the BPP. The same author identified another
Nb–Ta oxide with less than 3.0 wt.% TiO2 + SnO2 as
being a “possible” occurrence of ixiolite, based only on
X-ray-diffraction evidence. Beurlen et al. (2003a, 2004)
described the first occurrence of high-Ti ixiolite in the
BPP, with chemical compositions in agreement with the
criteria suggested by Wise et al. (1998). In this paper,
mineral-composition data for six occurrences of primary
intergrowths of tetragonal and orthorhombic (Nb + Ta
+ Ti) oxides from the BPP are discussed in view of the
unusual compositions we encountered, in some cases
overlapping a compositional gap observed elsewhere
(Černý et al. 1998, Uher et al. 1998, Klementova &
Rieder 2004), and of their occurrence in the form of
a cuneiform or symplectitic intergrowth. The origin
of such intergrowths is still unclear; the authors cited
and Černý et al. (1981) have explained it as a result of
replacement, coeval growth, or exsolution.
The BPP, as defined by Scorza (1944), extends
over an area of approximately 75 3 150 km, in the
eastern–southeastern part of the Seridó Foldbelt – Rio
Grande do Norte Tectonic Domain, between 5°45’ and
7°15’ S and between 35°45’ and 37°W, in the states of
Paraíba and Rio Grande do Norte, in northeastern Brazil
(Fig. 1). The Seridó Foldbelt in this area consists of a
Paleoproterozoic gneissic–migmatitic basement and
a supracrustal sequence that comprises the Jucurutú,
Equador and Seridó formations of the Neoproterozoic
Seridó Group (Van Schmus et al. 2003). The Jucurutú
Formation, at the base of the sequence, is composed of
gneiss with amphibolite, marble and skarn intercala-
tions, followed upward by quartzites, meta-arkoses and
metaconglomerates of the Equador Formation, covered
by sillimanite – cordierite – garnet – biotite schists of
the Seridó Formation, with minor intercalations by
amphibolite and marble. The regional metamorphism
of the Seridó Group is of the low-pressure – high-
temperature Abukuma type and attained the amphibolite
facies (Lima 1986). Retrograde metamorphism to the
upper greenschist facies is observed locally, related with
the fourth tectonometamorphic phase (F4).
The formation of the rare-element-enriched granitic
pegmatites, according to Araújo et al. (2001, 2005), is
related to the late- to post-tectonic phase of granitic
magmatism (G4, according to the classification of
Jardim de Sá et al. 1981). Most bodies of the mineral-
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1369

Fig. 1.  The Borborema Pegmatitic Province on a simplified geological base-map adapted from Brasil (1998, 2002), showing
the location of the Nb–Ta–Ti-oxide-bearing pegmatites discussed in the text. PB: Paraíba state; RN: Rio Grande do Norte
state.
1370 the canadian mineralogist
ized (i.e., enriched in Ta, Be, Li or Sn minerals) granitic
pegmatites are intruded into biotite schists of the Seridó
Formation (±80% of over 750 known occurrences).
Others (±11%) are emplaced in the Equador Forma-
tion (Da Silva et al. 1995). The few remaining bodies
are hosted by gneiss, marble and skarn of the Jucurutú
Formation, by late G3 and G4 granites (Jardim de Sá
1994), or by gneiss and migmatite of the Paleoprotero-
zoic basement sequence.
A regionally developed symmetrical zonation in the
distribution of the mineralized pegmatites was postu-
lated by Cunha e Silva (1981, 1983). A very discon-
tinuous peripheral zone of the province is dominated by
REE-enriched pegmatites, followed inward by a zone of
Sn-bearing pegmatites, an intermediate zone dominated
by beryl-bearing pegmatites, and a central, beryl–
tantalite-bearing zone. In the central zone, some small
areas are distinguished by pegmatites with tantalum-
dominated mineralization. This zoning model is the
first attempt to distinguish different types of mineralized
pegmatites in the BPP on the basis of ore-mineral para-
genesis. The proposed zoning, however, does not fare
well in a statistical evaluation because in the so-called
Sn zone, there are many bodies of granitic pegmatites
devoid of cassiterite, and exploited only for tantalite
and tapiolite. Also, cassiterite is a common accessory
phase coexisting with columbite-group minerals in the
central Ta–Be zone (Da Silva et al. 1995). A central
source pluton, which would be expected, either does
not exist or is not exposed. This regional model also
conflicts with the general pattern usually followed in
other pegmatite provinces, in which the degree of frac-
tionation of the pegmatite-forming magma increases
with the distance from the center of the pegmatite field,
and in which the REE-rich pegmatites are the closest
to the source, followed successively outward by beryl-,
beryl–columbite-, Li–Ta–(Sn)-mineralized pegmatites
and quartz veins (Varlamoff 1959, Schneiderhöhn 1961,
Černý 1989a, 1989b). Thus the concept of regional
zonation of Cunha e Silva (1983) is not accepted in the
local literature.
Four subtypes of Neoproterozoic (“Brasiliano
Cycle”) granites, related to the phases G3 and G4
of Jardim de Sá et al. (1986), occur in the area as
several independent intrusions of seemingly random
distribution. Field relationships do not show a corre-
lation between the pegmatite mineralization and the
intrusion(s) of a particular type or subtype of granite.
Lacking a potential parent granite, Ebert (1970) postu-
lated an anatectic origin of the mineralized pegmatites
of the area.
Most authors, however (Jardim de Sá et al. 1981, Da
Silva 1993, Da Silva et al. 1995, Araújo et al. 2001),
agree that small stocks (usually less than 0.3 km2 across
but, in two cases, reaching respectively 5 and 40 km2
in area), of leucocratic (sterile) pegmatitic granites
(attributed to the G4 phase of granitic magmatism of
Jardim de Sá et al. 1981), synchronous with (F4), are
the most probable parental granites of the mineralized
pegmatites, owing to their peraluminous character and
trace-element geochemistry (Da Silva 1993). These
usually small, discoidal or tabular intrusions of pegma-
titic granite present the same four petrographic facies
(banded aplite, graphic quartz – K-feldspar phenocrysts,
pegmatite and equigranular facies) that characterize
similar plutons considered to be the source of mineral-
ized pegmatites in other pegmatite fields throughout the
world (Černý et al. 2005). No larger body of granite was
so far recognized as the source for these small stocks
of pegmatitic granite in the BPP either.
Ages [U/Pb (uraninite) and Rb/Sr] of the pegmatites
(Ebert 1969, Almeida et al. 1968) indicate its formation
between 450 and 530 Ma. The Ar/Ar ages obtained on
biotite (Araújo et al. 2005) and U/Pb ages obtained on
columbite (Baumgartner et al. 2001, 2006), obtained
for pegmatites of the BPP, are 518–525 and 509–515
Ma, respectively.
The gaps between these pegmatite ages and U/Pb
ages obtained for the largest G3 batholith positioned
more or less in the center of the Seridó foldbelt, e.g.,
565 Ma (Jardim de Sá 1994) and 577 Ma (Legrand et
al. 1991), disqualify this granite type as possible source
for the mineralized pegmatites. Another age, of 528 ±
12 Ma (U/Pb on monazite), obtained by Baumgartner
et al. (2006) on a peraluminous pegmatitic granite
intrusion of the G4 phase, 1.2 km west of the town
of Carnaúba dos Dantas, RN, is considered by these
authors also to be too old to be considered a possible
source of the pegmatites.
The Internal Zonation
and Classification of the Pegmatites
The pegmatites of the BPP were first classified on
the basis of the internal zonation observed in the field
as homogeneous (usually sterile, generally concordant,
without internal structure) or heterogeneous, commonly
mineralized pegmatites (Johnston 1945). Later, the
designation “intermediate” (Rolff 1946) or “mixed”
(Roy et al. 1964) was introduced for those mineralized
pegmatites that show an incomplete or unclear pattern
of internal zonation. This designation is of quite dubious
merit, because it is locally used both in the case of
poorly fractionated pegmatites and for those highly
fractionated mineralized pegmatites where the original
zonal structure was partially or completely erased by
late episodes of replacement. Another problem with
the classification of the pegmatites according to their
internal structure is that the zonation pattern and mineral
paragenesis clearly change along the vertical or hori-
zontal extent of individual bodies of pegmatite. The
Boqueirão pegmatite in the BPP is a typical example
of a “heterogeneous” Ta–Li-bearing pegmatite in which
a strong longitudinal change of the internal zonation
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1371
pattern is observed. The geological map of this pegma-
tite (Fig. 2 in Beurlen et al. 2007) strongly resembles the
compact model of pegmatites with different degrees of
fractionation in a single body by Vlasov (1952).
A first attempt to classify and evaluate the degree of
fractionation of the pegmatites of the BPP on the basis
of mineralogy and trace-element geochemistry of the
feldspars and micas was based on ten bodies of mineral-
ized pegmatites (Da Silva 1993, Da Silva et al. 1995).
These findings indicate a poor to moderate degree of
differentiation; these bodies are of the beryl – columbite
– phosphate subtype of the rare-element pegmatite class
and LCT family (Černý 1991, Černý & Ercit 2005,
Martin & De Vito 2005). More recently, compositional
data on tourmalines, garnet and spinel (gahnite), and
trace-element geochemical data on micas and feldspar
(Soares 2004), indicate a higher degree of fractionation
for two other mineralized pegmatites, Quintos and
Capoeira 2, which are classified as examples of the
spodumene or lepidolite subtype (Soares et al. 2004).
According to Johnston (1945), a typical “hetero-
geneous” (zoned) and mineralized granitic pegmatite
of the BPP may present the following zones, from the
margins to the center: Zone I, typically composed of
comb-textured muscovite (in some cases tourmaline,
or platy ferrocolumbite, or biotite also are observed)
intergrown with medium-grained albite–oligoclase and
quartz; Zone II, formed by a homogeneous medium-
grained K-feldspar + quartz ± albite pegmatite with
common graphic intergrowths of quartz and perthite,
showing an inward increase in grain size; Zone III is
composed almost exclusively by large perthite crystals
(blocky feldspar zone), and Zone IV, a monomineralic
core of massive (milky or rose) quartz. This schematic
model of the internal structure is almost identical to
the worldwide accepted model (proposed by Cameron
et al. 1949) composed, respectively of the border, wall,
intermediate and core zones.
The main characteristics of the ixiolite-bearing
pegmatites chosen for study are summarized in Table 1.
They include heterogeneous pegmatites with four well-
developed zones according to the model of Johnston
(1945), like Feio and Capoeira, and less strongly zoned
ones with only two or three zones. Some of them may
be classified as being of the complex spodumene or
lepidolite subtype or as beryl – columbite – phos-
phate subtype (Černý 1992) based on compositions of
minerals of the feldspar, mica, garnet, tourmaline, and
columbite groups (Soares & Beurlen 2003, Beurlen et
al. 2005b, 2007).
1372 the canadian mineralogist
Petrography
Oxides from the Canoa and Pitombeira pegmatites
The Canoa and Pitombeira granitic pegmatites are
both poorly differentiated and enclosed in a porphyritic
granite, in turn intruded into biotite schists. They form
strings of lenses, with the individual bodies reaching a
maximum thickness in the order of 10 meters and the
longitudinal extent usually along thirty to a hundred
meters. They do not show a border zone, and are
dominated by a wall zone. A discontinuous, thin inter-
mediate zone envelops meter-sized lenses and pockets
of “quartz core”. The pegmatites were mined mainly
for feldspar and beryl, variety aquamarine. Tantalum-
bearing rutile crystals in these pegmatites were found as
centimetric idiomorphic crystals in samples taken from
the dumps of the pegmatites (Fig. 2a). These samples
(HB06, HB19, HB32, HB32b) contain decimeter-sized
perthite–quartz aggregates with sporadic millimetric
crystals of garnet. In some cases, these aggregates
may contain also centimetric yellowish green crystals
of beryl enveloping partially, together with quartz, the
idiomorphic crystals of Ta-bearing rutile. Therefore, the
rutile crystals are considered to be primary (crystallized
from the melt together with the essential components
of the pegmatite). This association is typically found
at the transition between the wall and intermediate
zones. In some cases, the Ta-bearing rutile crystals
are zoned, with a homogeneous core, surrounded by a
cuneiform intergrowth of Ta-bearing rutile with slightly
lower (Ta + Nb)/Ti values than in the core, but with
lamellar to bleb-shaped inclusions of titanian ixiolite,
oriented along three preferential crystallographic direc-
tions (Figs. 2b, c). The estimated modal proportion of
the Ta-bearing rutile host and the ixiolite lamellae in
this intergrowth is 4:1. Černý et al. (1981) referred
to similar intergrowths as “symplectitic niobian rutile
and columbite” surrounding homogeneous patches
of niobian rutile. The symplectites are considered to
be the result of simultaneous crystallization of both
phases, shielded against late fluids that could promote
re-equilibration. In addition to the supposedly primary
zoning from homogeneous cores to symplectitic rims,
both Ta-bearing rutile and ixiolite in the samples from
the Canoas and Pitombeira bodies, may be replaced by
an intergrowth of manganoan ilmenite, microlite and
niobian titanite at the borders of these crystals. As this
peripheral replacement partially overlaps the primary
zoning, the possibility that the cuneiform intergrowth
described is an intermediate product of alteration,
instead of being primary in nature, cannot be ruled out
completely.
Other associated opaque minerals found in a
heavy-mineral concentrate of the Pitombeira pegma-
tite (sample HB06) are tabular crystals of manganoan
ilmenite (with scandian–titanian manganocolumbite,
hematite and cassiterite as exsolution lamellae), magne-
tite, bismuthinite and very rare ferrocolumbite (Beurlen
et al. 2006).
Oxides from the Capoeira pegmatite
The Capoeira pegmatite, up to 50 m in width and 300
m in longitudinal extent, cross-cuts metaconglomer-
ates. It is a well-zoned body, with a dravite-rich border
zone, followed by a wall zone several meters thick,
grading into an intermediate zone formed exclusively
of K-feldspar with replacement pockets of muscovite
and selvages of bladed albite, and large lenses of quartz
in the core. The pegmatite was mined for feldspar
with a subordinate production of beryl, tantalum ore
concentrate (microlite and columbite-group minerals),
amblygonite and spodumene. Some smaller bodies,
possibly apophyses parallel to the main body, are
famous for the production of bright-blue gem-quality
elbaite, known in the literature as “Paraíba Tourmaline”.
A two-centimeter large crystal of niobian rutile (sample
HB21) was found in the elluvium of the pegmatite,
together with several crystals of manganocolumbite
(with the same composition as a manganocolumbite
crystal collected in the wall zone of the pegmatite).
The crystal of niobian rutile shows a consistent graphic
or cuneiform intergrowth with titanian ixiolite, with a
constant modal proportion of rutile to ixiolite, approxi-
mately 3:1, and sparse lamellae of manganocolumbite.
The nature of this intergrowth is well illustrated by the
back-scattered electron image (BSEI), which docu-
ments a gradual darkening (depletion of Ta) of the
host close to the included phase (richer in Ta and Nb
than the host) (Fig. 3). Similar features are typically
found in exsolution textures, according to Ramdohr
(1969). The ixiolite lamellae, up to 600 mm long, are
oriented along three crystallographic directions of
the niobian rutile host. A similar host–guest relation
between niobian rutile and ferrocolumbite found in the
Greenbushes pegmatite, Australia, was interpreted as
an exsolution texture by Klementova & Rieder (2004).
Noteworthy, and an additional argument to support the
formation by exsolution, is the similarity of the modal
host–guest proportion found by Klementova & Rieder
(2004) around 3:1, and with those of the samples from
the Canoa (HB19 and HB32) and Pitombeira (HB06)
pegmatites, described above.
Oxides from the Alto Feio pegmatite
The Alto Feio pegmatite is a large, well-zoned body,
composed of a wall zone, an intermediate zone and a
large quartz core, mined for rose quartz and feldspar,
with insignificant production of Nb–Ta oxides nowa-
days; during the early 1940s, four tonnes of Ta-ore
concentrates were produced. A heavy-mineral concen-
trate dominated by ferrocolumbite grains includes a
2-mm-large composite crystal (sample HB0408) that
shows a compositional growth-zoning, with a core
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1373

Fig. 2.  a) Polished section (HB3201B) and samples of Ta-bearing rutile crystals with inclusions of high-Ti ixiolite from the
Canoa pegmatite (scale bar in cm). b) Photomicrograph of a polished section of a Ta-bearing rutile crystal (sample HB3201B)
at the transition from a homogeneous core, in the lower part, to a heterogeneous border, with lamellar inclusions of ixiolite
along three directions in a Ta-bearing rutile matrix, in the upper part, in plane-polarized reflected light. The lamellar inclu-
sions of ixiolite are considered to be of exsolution origin. c) The same exposure, shown in cross-polarized reflected light. d)
The same exposure with BSEI–EDS. Note that the hosting rutile becomes darker (depleted in Nb–Ta) close to the ixiolite
lamellae. Scale bar is 200 mm wide.

of Ta-bearing rutile and a rim of ferrotitanowodginite
(Fig. 4). This grain contains also some small inclusions
of cassiterite.
Oxides from the Quintos pegmatite
The Quintos pegmatite extends over about 150
m north–northwest, with a thickness of up to 30 m,
cross-cutting quartzite. It is composed of a well-
defined border zone, beginning with an aplitic array
of quartz, K-feldspar and albite grains, with dravite,
apatite and muscovite as accessory minerals, grading
into a zone dominated by comb-textured dravite–
quartz intergrowths. The border zone grades into
the albite-, quartz-, K-feldspar-dominated wall zone
with sporadic large crystals of dravite and muscovite.
The intermediate zone mainly consists of albite and
replacement bodies (muscovite, bladed albite, elbaite
1374 the canadian mineralogist
and lepidolite), with a few partially preserved blocky
crystals of K-feldspar and sporadic tabular crystals of
spodumene. In the center, there are lenticular bodies of
massive quartz with rosettes of the gem-quality light
blue “Paraíba” tourmaline. According to geochemical
data on feldspars, micas, garnet, tourmaline and gahnite
(Soares et al. 2004, 2007), the degree of fractionation
reaches the highest level so far observed in the BPP.
Some idiomorphic, tabular crystals of ixiolite
(sample QB8) were collected in the wall zone (Fig. 5a).
The crystals show growth zoning with strong oscillatory
compositional variations, as seen under the scanning
electron microscope (Fig. 5b), with a niobium-rich rim
(niobian rutile) and Ta-rich core (titanian ixiolite). The
zonation under the optical microscope is only recog-
nized by variation in frequency and intensity of internal
reflections and anisotropy, which are more intense in
the rutile rim. The EMPA data with 20 mm equidistance
along a section across the crystal in Figure 5c illustrate
a complex combination of the mechanisms of cation
substitutions responsible for the oscillatory composi-
tional variation. These mechanisms were discussed in
detail by Beurlen et al. (2003a). The main mechanisms
involved are the homovalent substitutions Fe2+ ⇔ Mn2+
and Ta ⇔ Nb, and the coupled heterovalent substitu-
tion 2Ti ⇔ Fe3+ + (Nb,Ta) and 3Ti ⇔ (Fe,Mn)2+ +
2(Nb,Ta). These mechanisms were also identified by
other authors in ixiolite (or columbite) and Nb-bearing
rutile (e.g. Černý et al. 1981, 1998, Uher et al. 1998,
Fig. 3.  Back-scattered electron (BSE) image of an inter-
growth of niobian rutile (dark gray) hosting cuneiform
inclusions of titanian ixiolite (gray, point 3) and rare man-
ganoan ferrocolumbite (light gray, almost white, point 4).
All phases where identified by transmitted electron diffrac-
tion (FIB and HRTEM) and EMPA. Note that the niobian
rutile matrix is darker (depleted in the heavier elements Ta
and Nb) in the immediate neighborhood of the ixiolite and
columbite inclusions (e.g., at points 1 and 5) than in areas
farther from the inclusions (e.g., point 2). This feature
strongly suggests formation by exsolution. Sample HB21.
The scale bar is 200 mm.
Klementova & Rieder 2004). In the present case, the
mechanisms act with variable intensity and direction
of oscillation during the interval of crystal growth. The
main active mechanisms along the analytical section
(line L7) shown in Figure 5c [points L7–1 (rim) to
L7–36 (core) and L7–41 (core) to L7–84 (rim); points
37 to 40 are omitted for simplicity and correspond
to Ca-bearing manganocolumbite inclusions], are
discriminated below:
L7–1 to L7–7: 3Ti ! Fe2+ + 2Nb (rutile rim)
L7–7 to L7–10: 2Ti ! Fe3+ + Nb;
L7–10 to L7–14: 2Ti ! Fe3+ + Ta;
L7–11 to L7–14: Fe2+! Mn2+;
L7–14 to L7– 19: 2Ti ! Fe3+ + (Nb,Ta);
L7–19 to L7– 26: 3Ti ! Fe2+ + 2Ta, and Nb ! Ta
(inner rutile rim);
L7–26 to L7–29: 2Ti ! Fe3+ + (Nb,Ta)
(transition rutile – ixiolite);
L7–29 to L7–31: 3Ti ! (Fe,Mn)2+ + 2(Ta,Nb)
(ixiolite core);
L7–31 to L7–36: ?Ti + Fe3+ ! Fe,Mn) + (Ta,Nb)?
(ixiolite core);
Fig. 4.  BSE image of a zoned Ta-bearing rutile crystal (dark
gray, points 3 and 4) overgrown and replaced by an also
zoned ferrotitanowodginite border (light gray, points 1 and
2). The crystal (HB0408) was found in a heavy-mineral
concentrate of the Alto Feio pegmatite. The other grains
in the heavy-mineral concentrate mainly consist of ferro-
columbite. The scale bar width is 200 mm. The identifica-
tion of the mineral phases is based on EMPA and electron
diffraction, using HRTEM and FIB.
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1375

Fig. 5.  a) Sample of the contact of the Quintos pegmatite with the quartzites at the base (banded, gray) showing the border
zone with a cm-thick aplitic band followed upward by comb-textured black dravite and the coarser-grained wall zone formed
by K-feldspar, albite, quartz and sparse (dark) muscovite and dravite crystals and a tabular grain of ixiolite (arrow) at the
transition to the intermediate zone at the top. Scale bar at the top: 7 cm. b) BSE image of a fragment of a composite crystal
(sample QB08), with a titanian ixiolite core (light gray) with oscillatory compositional zoning, overgrown by niobian rutile
rim (dark gray). The phase identification was confirmed by X-ray diffraction (powder method) and EMPA. A EMPA cross-
section A–B with data-point equidistance of 20 mm, for a total of 84 analyses, allowed us to identify the main mechanisms
of substitution responsible for the compositional zoning. Scale bar: 200 mm. The grain is part of a tabular crystal in the wall
zone of the Quintos pegmatite (sample photo in Fig. 5a). The EMPA section is shown in Fig. 5c. c). EMPA cross-section across
the composite ixiolite – niobian rutile crystal of Figures 5a and 5b, with data-point equidistance of 20 mm. The oscillatory
compositional growth-zoning reflects the oscillatory sense and intensity of the following main mechanisms of substitution,
as discussed in detail by Beurlen et al. (2003a): 1) Nb ! Ta; 2) 3Ti ! [(Fe,Mn2+) + 2(Ta,Nb)]; 3) 2Ti ! (Fe3+ + Ta).
1376 the canadian mineralogist
L7–36 to L7–41: Nb+Fe3+ ! 2Ti (ixiolite core);
L7–41 to L7–48: Nb ! Ta and Ti + Fe3+ !
(Fe,Mn)2+ + Ta (ixiolite border);
L7–48 to L7–74: Ta ! Nb and ?(Fe,Mn) + Ti !
2Fe3+? (ixiolite rim);
L7–75 to L7–84: Ta ⇔ Nb and 2 Ti = Fe3+ + Ta
(rutile rim).
This complex alternation and variable intensity of
different mechanisms of substitution provide strong
evidence for rapid growth of the crystals under disequi-
librium conditions.
Alteration products of these crystals include
hematite, rutile, fersmite, microlite, uranmicrolite,
uranpyrochlore and zircon, commonly found in frac-
tures. A few idiomorphic inclusions of Ca–Ti-bearing
manganocolumbite also may occur. In replacement
bodies, sporadic compositionally zoned primary crystals
of cesian natrobistantite–uranmicrolite up to 1 cm in
size were found, in some cases with lamellar inclusions
of bismutotantalite and microlite oriented along 111,
and inclusions of waylandite. Other common associ-
ated opaque minerals are ilmenite, manganocolumbite,
magnetite (with gahnite, ilmenite and rutile inclusions)
and rare brannerite (Beurlen et al. 2005a).
Oxides from the Roncadeira pegmatite
In the Roncadeira pegmatite, the internal zonation
is poorly developed, with a discontinuous quartz–
muscovite-rich border zone, an albite-rich, and in some
cases aplitic, wall zone, grading into a very locally
developed intermediate zone with some larger blocky
feldspar crystals growing into also sparse and small
quartz lenses representing a discontinuous core. The
pegmatite forms a string of lenses, each a decimeter to
meter wide and a decameter long. Some submillimetric
idiomorphic composite crystals of high-Ti ixiolite and
ferrotantalite are found in association with disseminated
cassiterite in the border zone of the pegmatite. The
border zone consists of an aggregate of quartz – feld-
spar – muscovite – sillimanite. In the high-Ti ixiolite
grains referred to in this paper (sample HB24B), we
have commonly observed a compositional zonation,
beginning with ferrotantalite compositions in the core,
and culminating with high-Ti ixiolite composition in
the rim. The oscillatory variation in composition and
the idomorphic shape of the crystals against quartz +
feldspar, as shown in the example in Figure 6, support
the primary nature of the crystals and of the zonation.
Cassiterite in this pegmatite occurs also in larger,
centimetric crystals in the wall zone. The cassiterite
crystals commonly contain an ultra-fine “emulsion” of
exsolution-induced cloudy ferrowodginite, ferrotapi-
olite and manganocolumbite blebs and lamellae, and
sporadic Ta-bearing rutile inclusions, with up to 53
wt.% Ta,Nb2O5 (samples HB24B and HB40). Results
of EMPA analyses of these commonly submicroscopic
intergrowths (the size of the blebs and lamellae is
commonly below 0.1 mm, Beurlen et al. 2003b) may
simulate a consistent “staringite” (IMA-discredited
name of a supposedly Ta-rich cassiterite, Groat et al.
1994) composition (12 to 18 wt.% Ta2O5).
Analytical Methods
Polished sections of crystals and heavy-mineral
concentrates (embedded in acrylic resin) were prepared
and studied petrographically. Conventional X-ray
diffractograms were obtained using a D–5000 Siemens
X-ray diffractometer and a CuKa tube in the Depart-
ment of Fundamental Chemistry of the Federal
University of Pernambuco. Those samples showing
phases other than columbite–tantalite-group minerals or
cassiterite were submitted for more detailed analyses by
scanning electron microscope (SEM–EDS) to confirm
the phase identification. Samples from six out of 28
pegmatite bodies studied revealed niobian or tantalian
rutile intergrown with titanian ixiolite. The additional
confirmation of the titanian phases (ixiolite, rutile and
wodginite) occurring as very fine grained intergrowths,
as in the case of the Capoeira, Feio and Roncadeira
pegmatites, was possible by the use of high-resolution
transmission electron microscopy (HRTEM) and a
focused ion-beam (FIB) nano-sampling device in the
GeoForschungsZentrum Potsdam, Germany, following
the procedure described by Wirth (2004).
Fig. 6.  Idiomorphic (thus primary) composite crystal (sample
HB24B4) enclosed in an aggregate of quartz, albite and
sillimanite (black), from the border zone of the Roncadeira
pegmatite, hosted by biotite schists. The light gray, compo-
sitionally zoned core of the crystal consists of ferrotantalite
(points 6, 7 and 8), and the dark gray border, also zoned,
consists of titanian ixiolite (point 9). The phase identifica-
tion is based on EMPA, and HRTEM + FIB. The scale bar
is 10 mm long.
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1377
The SEM analyses were made at the University
of Campinas São Paulo using a SEM Leo 430i,
Cambridge, EDS model Cat. B, using the following
working conditions: 20 kV, 30 seconds acquisition time,
using the following standards: Ta (TaMa), Nb (NbLa),
Sn (SnLa), Ti (TiKa), V (VKa), Sb (SbLa), Bi (BiMa)
Zr (ZrLa), U (UMa), Hf (HfMa), PbF2 (PbMa), BCR2
(FeKa, MnKa, AlKa, CaKa, NaKa, SiKa, KKa).
Preliminary EMP data were obtained with a JEOL
JXA–8600 instrument operated at 20 kV, 40 nA, with
acquisition times of 20 s for major, 30 s for minor and
40 s for trace elements and the following standards:
TiO 2 (TiKa), Nb (NbLa), Ta (TaMa) Sn (SnLa),
anorthite (AlKa), olivine (FeKa), wollastonite (CaKa),
spessartine (MnKa), Bi (BiMa), in the EMP lab of the
University of São Paulo (USP), Brazil.
Follow-up EMPA were made at the GeoFor­
schungsZentrum Potsdam, using a Cameca SX50 and
SX100 electron microprobe at 20 kV and 40 nA, with
acquisition times of 20 s for FeKa, MnKa, TiKa, ScKa,
MgKa, AlKa, CaKa, NaKa, SiKa, KKa, 30 s for
NbLa, SnLa, SbLa, ZrLa HfMa, YLa, CsLa, BaLa,
and 50 s for TaLa, BiMa, UMa, PbMa, ThMa, CeLa,
LaLa, using the following standards: albite (Na), ilme-
nite (Fe Ti), cassiterite (Sn), orthoclase (K,Al), titanite
(Si,Ca,Ti), zircon, metallic Nb, Ta, Th, U, vanadinite,
BaSO4, CePO4, LaPO4, YPO4, ScPO4, InSb, MgO,
HfO2, MnTiO3, Bi2S3, and pollucite. Only results with
analytical total between 102 and 98 wt.% were used, but
the great majority of the datasets have totals between
99 and 101%.
The calculation procedure to obtain the cation
proportions in atoms per formula unit (apfu) was, in a
first step, to normalize them to a sum of 24 oxygen ions
for most oxides, to allow an easier comparison of the
results. In a second step, where the cation sum exceeds
the theoretical value (12 for phases of the columbite,
tapiolite, and ixiolite groups, and niobian or tantalian
rutile), the Fe2+ content was partially converted to Fe3+
(cf. Ercit et al. 1992a, b) by trial and error until the
cation sum reached the value of 12.0000 ± 0.0002.
The effectiveness of this procedure was checked by
repeating some calculations using the method proposed
by Droop (1987).
According to Černý et al. (1998), a distinction
between ixiolite and columbite-group minerals by
X-ray data is possible only after heating the mineral
for at least 16 hours above 1,000°C. Wise et al. (1998)
proposed a chemical distinction between ixiolite and
columbite-group minerals only for ixiolite samples
with more than 10 mol.% TiO2 + SnO2. Therefore, the
distinction among the columbite, wodginite and ixiolite
groups was made using the stoichiometry criteria
suggested by Wise et al. (1998). For this purpose, the
general formula of wodginite is taken to be A3B3C6O24,
instead of A4B4C8O32, for comparison with other oxides,
with general formulas A 4C 8O 24 for columbite and
(A,B,C)12O24 for ixiolite, and B12–12xA4xC8xO24 (x <
0.65) for rutile. In the wodginite formula, A stands for
(Fe,Mn,Ca,Mg)2+, Li and vacancy, B stands for Sn, Ti,
Zr, Hf, Fe3+, Sc and cTa excess, and C stands for Nb, W
and Ta. The Fe3+ in this case is calculated to complete
the B + C sites to 9.0000, according to Ercit et al.
(1992a). The label ixiolite is assigned to those samples
with more than 10 mol. % TiO2 + SnO2 + Sc2O3 that
did not fit the criteria for wodginite: Ta ≥ 2Nb at the C
site, B-site cations Ti, Sn, Sc, Fe3+ ≤ 0.5 Ta+Nb+W, and
Ti, Sn, Sc, Fe3+ + Ta excess in C = 3 apfu, according to
Ercit et al. (1992a).
Compositional Variations of the Minerals
Selected representative data of the coexisting
Nb–Ta–Ti oxides are listed in Table 2. The complete
dataset is available from the Depository of Unpublished
Data on the MAC web site [document Borborema
cm45_1367].
Variation of Ta and Mn values
In terms of Ta/(Ta + Nb) and Mn/(Mn + Fe) values,
mineral phases assigned to the ixiolite group present
a more or less random distribution within and closely
surrounding the ferrocolumbite and ferrotapiolite fields.
They, however, avoid the field of the compositional
gap between ferrotapiolite and ferrotantalite (a gap that
corresponds to the usual compositions of the classical
wodginite phases) almost completely (Fig. 7). This is
an indication that, if a wodginite-group phase occurs
in this dataset, in this case as ferrotitanowodginite, it is
rather an exception than the rule. For comparison, some
data on true ferrowodginite (Sn dominant at the B site),
which occur as blebs and lamelar inclusions in cassit-
erite that probably formed by exsolution and coexisting
with the ixiolite, also are plotted in the diagram.
The columbite-group phases coexisting with the
ixiolite–rutile association occur as sporadic inclusions
in the case of QB08 and HB21, as independent grains
(HB04, HB21 and HB06), and in the core of zoned
grains of ixiolite in the case of HB24B. They invari-
ably have higher Nb/(Nb + Ta) and usually higher Mn/
(Mn + Fe) values than the coexisting ixiolite. The only
exception is a single grain of ferrocolumbite in the
HB06 heavy-mineral concentrate; all other inclusions
of columbite in the same sample (in this case exsolu-
tion lamellae, paired with cassiterite and hematite) in
coexisting ilmenite also are richer in Mn and Nb than
the ixiolite.
The rutile-group phases coexisting and intergrown
with the ixiolite usually present higher Fe/(Fe + Mn)
and Ta/(Ta + Nb) values than the adjacent ixiolite, indi-
cating a systematic enrichment of Fe and Ta in favor of
the tetragonal and Ti-richer phases, as already observed
by Černý et al. (1998). This is the case of sample HB04
1378 the canadian mineralogist
(zoned composite crystal with a Ta-bearing rutile core
and ferrotitanowodginite rim, both plotting in the field
of ferrotapiolite), samples HB06 and HB19 (crystals
of Ta-bearing rutile, with data plotting in the field of
ferrotapiolite, with cuneiform to vermicular inclu-
sions of titanian ixiolite, plotting in the field of ferro-
columbite). This is also the case of sample HB24B (a
zoned composite crystal with a ferrotantalite core and a
titanian ixiolite rim, with data plotting in the ferrotapi-
olite field) and of the sample HB21 (crystal of niobian
rutile with cuneiform inclusions of titanian ixiolite,
interpreted as exsolution bodies). An exception to this
“fractionation rule” are the crystals with oscillatory
growth-zoning from the Quintos pegmatite (sample QB
08) with a high-Ti (and high-Ta) ixiolite core (the data
plot in the ferrotantalite field) grading almost continu-
ously to a border of niobian rutile, richer in both Fe
and Nb, near the composition of the ferrocolumbite
end-member.
In addition to the large compositional spread of
the whole ixiolite- and rutile-group datasets in the
columbite quadrilateral, a great difference in the extent
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1379
of fractionation of the coexisting phases is observed,
as reflected in the width of the compositional gap
between coexisting rutile and ixiolite phases. This is
true also for pairs of data points obtained close to the
contact between the coexisting phases, connected in the
diagram (Fig. 7a) by dotted lines. This gap is very wide
in the cases of HB06 and HB09. It is much narrower,
but still evident, in the cases of HB21 (the inferred
exsolution-lamellae of ixiolite plot in the Ta-poor area
of the ferrocolumbite field), HB24 (zoned crystal with
Ti-rich phase in the ferrotapiolite field and the Ti-poor
phase in the ferrotantalite field), and HB04, but almost
absent in the case of QB08 (Fig. 7b). The observed gaps,
therefore do not reflect a simple temperature-dependent
miscibility gap between rutile (richer in Fe and Ta) and
ixiolite (richer in Mn and Nb), but may result from
disequilibrium conditions during crystallization. This is
certainly true in the case of the zoned crystals HB–04,
HB24B and QB08, and with more reason for the last
two, whose Ti-poor phases plot in the area of the gap
observed for the cases HB06 and HB19.
1380 the canadian mineralogist

Fig. 7.  EMPA data on members of the rutile and ixiolite groups and other coexisting Ti–Ta–Nb oxides (mainly columbite
and wodginite groups) in six pegmatites from the BPP, plotted in the “columbite quadrilateral” [Ta/(Ta + Nb) versus Mn/
(Mn + Fetotal)]. The analytical data for grains of different phases in direct contact are connected by dotted lines. Some data
pertaining to coexisting ferrotapiolite, columbite and wodginite from the same occurrences are also plotted for comparison.
Mineral abbreviations in the legend of this and the following figures are defined in footnotes to the tables. Wdg(Ti) stands
for ferrotitanowodginite, Rt(Ta) for Ta-bearing rutile, Rt(Nb) for Nb-bearing rutile, Ixl(Fe) for a possible ferri-ixiolite (or
“ferri-ferriwodginite”), and Ftp(Ti) for titanian ferrotapiolite.
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1381

Fig. 8.  Plot of the same EMPA data as Figure 7, here in the triangular (Nb,Ta) – (Sn,Ti) – (Mn,Fe) diagram. For comparison,
data by Uher et al. (1998) and Černý et al. (1998) for tetragonal and orthorhombic Nb–Ta–Ti oxides are shown as dotted
or continuous gray bars near the columbite – rutile and Fe3+NbO4 tie-lines. Note that many of the BPP data fall in the area
forming a gap between tetragonal and orthorhombic phases in the data by Uher et al. (1998) and Černý et al. (1998) Note
also the location of some data points (HB24A, “ixiolite or ferri-ferri-wodginite?”) very close to the Fe3+TaO4 end-member,
where no natural phase is known.

Variation of the (Nb,Ta), (Fe,Mn), (Ti,Sn), Ti
and Sn values in triangular diagrams
The great variation in the compositional gap between
coexisting tetragonal and orthorhombic phases becomes
evident also in the triangular plot (Nb,Ta) – (Ti,Sn) –
(Fe,Mn) (Fig. 8). In this diagram, the data for ixiolite
HB21 partially overlap the composition of niobian rutile
QB08. Note also that data for ixiolite HB21, ixiolite
QB08 and rutile, and ixiolite HB24B in this diagram,
owing to higher Ti-contents in ixiolite and to higher
(Ta + Nb) contents in the tetragonal phases, occupy
a position where Černý & Ercit (1989), Černý et al.
(1998) and Uher et al. (1998) found a rutile–ixiolite
compositional gap in similar intergrowths from other
pegmatite provinces. This diagram also shows that all
HB21 and QB08 data and the rutile data of HB06 and
HB19 fall very close to the rutile – Fe3+(Nb,Ta)O4 tie-
line, indicating 3Ti ⇔ (Fe,Mn) + 2(Ta,Nb) and (Fe,Mn)
+ (Ta,Nb) ⇔ Fe3+ + Ti (for ixiolite) and 2Ti ⇔ (Ta,Nb)
+ Fe3+ (for rutile) as main mechanisms of substitution,
simultaneously with the simple isovalent Fe–Mn and
Ta–Nb substitutions, not observable in this diagram.
The important participation of Fe3+ (calculated in every
1382 the canadian mineralogist

Fig. 9.  Plot of the same EMPA data as in Figure 7, here in terms of (Ti,Sn) – Nb – Ta. Again, the datapoints of “paired phases”,
obtained near of the grain contact, are connected by dotted lines. If all data are considered, no possible solvus area can be
identified, but if the data of sample QB08 are not considered, a large solvus area may be suggested in the middle of the
diagram, and a smaller solvus close to the (Ti,Sn) – Nb edge (sample HB 21) in the upper part (Ti-rich) of the diagram and
an also narrower solvus close to the (Ti,Sn) – Ta edge, here in the lower, Ta-rich, part of the diagram (Samples HB04 and
HB24). Fields of the compositions for different phases are separated by dashed thick gray lines.

phase in this paper according to Ercit et al. 1992a) in
this mechanism of substitution may be indicative of
high oxygen fugacity in this case. On the other hand,
all HB04 data and HB06 and HB19 ixiolite plot close
to the rutile – wodginite – columbite tie-line, suggesting
(Fe,Mn) + 2(Ta,Nb) ⇔ 3(Ti,Sn) as the main mechanism
of substitution (at low oxygen fugacity), whereas the
HB24B data occupy an intermediate trend (and an
intermediate oxygen fugacity). Another group of data
for sample HB24A, determined earlier as ferrotantalite,
occupies a position very close to the Fe3+(Nb,Ta)O4
end-member and could possibly be classified as “ferri-
ferri-wodginite” if the classification criteria suggested
by Ercit et al. (1992b) for the wodginite group were
applied. Another possibility would be to classify this
composition as a “ferri-ixiolite”. In both cases, no
known natural samples match this composition. This
phase occurs, together with microlite, as a product of
alteration of ferrocolumbite crystals, along cleavages
and fractures. Electron-diffraction patterns (HRTEM)
will be necessary to provide a definitive identification
in this case.
The triangular diagrams (Ti,Sn)–Nb–Ta and Ti–Nb–
Ta (Figs. 9, 10) allow a better view of the compositional
gaps between the coexisting Ti-rich and (Ta + Nb)-rich
phases (pairs of data close to the contacts are connected
by dotted lines). If the data of sample QB–08 are not
taken into consideration, the gaps seem to be much
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1383
Fig. 10.  Plot of the same EMPA data as Figure 7, here in terms of Ti – Nb – Ta, with the same symbols as in the previous
diagrams. For details, see text.
larger in the middle of these diagrams, in the region
where Ta and Nb occur in similar proportions, and
decrease with increasing or decreasing Ta/Nb values,
toward the Ti–Nb and Ti–Ta edges. It seems also that the
solubility of Ta in the tetragonal (Ti-dominant) phases
is greater than that of Nb, and that the Ti solubility is
larger in Nb-dominant orthorhombic phases than in
Ta-dominant phases. The position of the ixiolite data
for sample QB08 in the field of the compositional gap
in the middle of the diagram suggests that higher Fe3+
contents as shown in Figure 9 (higher oxygen fugacity)
enhances the solubility of Ti in the orthorhombic and
other (Ta + Nb)-dominant phases. The data for sample
QB08 form an almost continuous sinuous linear trend,
reflecting the oscillatory compositional growth-zoning,
with oscillating intensity and direction of mainly four
or even five different mechanisms of substitution, as
described earlier in this paper and in detail by Beurlen
et al. (2003a). If the pairs of data for host – exsolution
lamellae contacts in sample HB21 are examined sepa-
rately, it is possible to entertain the possibility that the
gaps between these phases shift together with the bulk
Ti–Ta–Nb proportions in the same crystal, maintaining
the width of the gap. If, instead, all data of the sample
are analyzed as a whole, they may simulate the absence
of a gap.
It remains unclear why in some cases the (Ta,Nb)-
dominant phase that coexists in direct contact with
the Ti-dominant phase is of the wodginite group, and
in other cases, it is of the columbite or ixiolite group.
Amongst the cases discussed in this paper, ixiolite
is more commonly observed in contact with Nb- or
Ta-bearing rutile than columbite or wodginite. This is
also the case in the occurrences of intergrowths inter-
preted as formed by exsolution, e.g., samples HB19,
HB06, HB21, HB32, from the Canoa, Pitombeira and
1384 the canadian mineralogist
Capoeira pegmatites. This seems also to be the predomi-
nant case in examples examined by Uher et al. (1998)
and Černý et al. (1998), whereas in the case reported
by Klementova & Rieder (2004), the exsolved phase is
considered to be ferrocolumbite.
A similar complexity occurs with the Ta–Nb-rich
exsolution-induced bodies frequently observed in
cassiterite, forming either wodginite, or ferrotapiolite or
columbite (Neiva 1996, Groat et al. 1994, Beurlen et al.
2003b). The observation of exsolution lamellae of ferro-
columbite in the core of one single crystal of cassiterite
by Beurlen et al. (2003b), and of ferrowodginite in the
rim of the same crystal, suggests that the solubility of
Ta in cassiterite is greater than that of Nb, and that the
solvus between ferrocolumbite and cassiterite may be
intersected earlier, probably at higher temperatures, than
the solvus between wodginite and cassiterite.
In addition to temperature and Ti/(Nb + Ta) values,
other factors like fugacity of oxygen (reflected in the
ratio Fe2+/Fe3+), Fe/Mn and Nb/Ta values and rate of
cooling may play an important role in the location and
extent of the solvus. More data are required to establish
the influence of the possible variables in the exsolution
process. Unfortunately, in the numerous cases examined
by Uher et al. (1998) and Černý et al. (1998), no distinc-
tion is made case by case, whether the “orthorhombic”
phase “coexisting with” or "exsolved in" rutile is of the
ixiolite or of the columbite group, and the analytical
data for those pairs supposedly formed by exsolution
are not listed.
Finally, apart from the invariably high Ti-content of
many of the analyzed grains of ixiolite, compared with
the data in literature, in two of the six cases studied, the
compositional zoning of the crystals indicates a reverse
geochemical evolution trend, with a late enrichment in
Ti–Nb–Fe at the expense of earlier compositions richer
in Ta–Mn. Similar reverse trends were also observed
elsewhere by Tindle et al. (1998) and Tindle & Breaks
(2000). Another pattern of behavior commonly inter-
preted as anomalous is the presence of early Ti-rich
Nb–Ta oxides. Elsewhere, such material is interpreted
as consequence of contamination of the pegmatite-
forming melt by assimilation of mafic wallrocks (Černý
& Nĕmec 1995, Uher & Broska 1995, Smeds et al.
1999). This interpretation does not find support in the
present case, because the wallrocks (quartzites, granites,
metaconglomerates) are depleted in mafic minerals.
Conclusions
Analytical data on titanian ixiolite and other
(Ta,Nb)-dominant phases and the intergrown niobian–
tantalian rutile from six occurrences of pegmatites in
the BPP reveal a variable width of the compositional
gap and variable bulk-compositions of these minerals,
which were found to be incompatible with a simple
temperature-dependent “solvus”. Data from four of the
analyzed occurrences (samples QB08, HB21, HB04 and
HB24) present unusual compositions and plot within the
compositional gap established by Uher et al. (1998) and
Černý et al. (1998) for similar intergrowths elsewhere.
The gaps and trends observed in this study seem, there-
fore, to be either the result of disequilibrium conditions
during crystallization (variable conditions of oxygen
fugacity, temperature, cooling rates and bulk composi-
tion) or of only partial re-equilibration during cooling,
or both, despite the cuneiform exsolution-like inter-
growths in three of the cases studied. The possibility
of disequilibrium during crystallization is in agreement
with the growth zoning observed in the three other
cases. The compositional variations observed in five of
the occurrences studied agree with the observations in
the literature, which indicate a Ta- and Fe-enrichment
favoring the tetragonal Ti-rich phases, and Nb and Mn
favoring the coexisting orthorhombic (or other Ta,Nb-
dominant) phases. However, in the sixth case (QB08),
Ta and Mn are enriched in an earlier core of ixiolite,
in comparison to the coexisting rim of rutile. This case
is also unusual because of the late enrichment in Ti,
Nb and Fe at the expense of Ta and Mn, representing
a reverse fractionation trend shared also by sample HB
24. It remains unclear why in some cases the (Ta,Nb)-
dominant phase coexisting in direct contact with the
Ti-dominant phase is of the wodginite or columbite
groups instead of the more usual ixiolite group.
Acknowledgements
This study was made possible owing to the financial
support of the Brazilian Research Council – CNPq,
through grants APQ 470199/01 and PQ 352181/92–3
and of CAPES (grant AEX 0728/04–7), which is
greatly appreciated. We are also indebted to Prof. Dr.
W. Heinrich of the GeoForschungsZentrum Potsdam
(GFZ) in Germany for the free use of the HRTEM and
microprobe facilities, to O. Appelt and G. Rhede of the
GFZ for the technical support associated with electron-
microprobe analyses, to Dr. Bernardino R. Figueiredo
of the Instituto de Geociências of the University of
Campinas, Brazil (IGE–UNICAMP) for authorization
of the SEM analyses at the IGE–UNICAMP. We thank
Claudio de Castro (Federal University of Pernambuco,
UFPE) for providing several samples for this study.
Dr. Robert F. Martin (McGill University, Montreal),
Mr. A.U. Falster (University of New Orleans) and two
anonymous reviewers and Dr. Gorki Mariano (UFPE)
are acknowledged for critical reading and very helpful
and constructive comments and discussion.
References
Adusumili, M.P.S. (1978): Nióbio-tantalatos do Nordeste do
Brasil: a série columbita–tantalita. Jornal de Mineralogia
7, 195-225.
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1385
Almeida, F.F.M., Melcher, G.C., Cordani, U.G., Kawashita,
K. & Vandoros, P. (1968): Radiometric age determina-
tions from northern Brazil. São Paulo. Soc. Bras. Geol.
Bol. 17, 3-15.
Araújo, M.N.C., Silva, F.C.A. & Jardim De Sá, E.F. (2001):
Pegmatite emplacement in the Seridó Belt, northeastern
Brazil: late stage tectonics of the Brasiliano Orogen. Gond-
wana Res. 4, 75-85.
Araújo, M.N.C., Vasconcelos, P.M., Silva, F.C.A., Jardim
De Sá, E.F. & Sá, J.M. (2005): 40Ar/39Ar geochronology
of gold mineralization in Brasiliano strike-slip shear zones
in the Borborema province, NE Brazil. J. S. Am. Earth
Sci. 19, 445-460.
Baumgartner, R., Moritz, R., Romer, R. & Sallet, R.
(2001): Mineralogy and U/Pb geochronology of beryl and
columbo-tantalite pegmatites in the Serido pegmatite dis-
trict, northeastern Brazil. In Mineral Deposits at the Begin-
ning of the 21st Century (A. Piestrzynski, ed.). Proc. 6th
Biennial SGA Meeting (Krakow). Balkema, Rotterdam,
The Netherlands (371-375).
Baumgartner, R., Romer, R.L., Moritz, R., Sallet, R. &
Chiaradia, M. (2006): Columbite–tantalite-bearing gra-
nitic pegmatites from the Seridó Belt, northeastern Brazil:
genetic constraints from U–Pb dating and Pb isotopes.
Can. Mineral. 44, 69-86.
Beurlen, H., Castro, C., Thomas, R., Da Silva, M.R.R.
& Prado-Borges, L.E. (2004): Strüverite and scandium
bearing titanian ixiolite from the Canoas Pegmatite (Acari
– Rio Grande Do Norte) in the Borborema Pegmatitic
Province, NE-Brazil. Est. Geol. 14, 20-31.
Beurlen, H., Da Silva, M.R.R., Silva, D., Wirth, R. &
Olivier, P. (2005b): Variação composicional de óxidos
de Nb–Ta–(Sn–Ti) como indicadores do potencial meta-
logenético na Província Metalogenética da Borborema. In
First Symp. Bras. Metalog., SBG Gramado-RS, Resumos
Expandidos, CD-ROM.
Beurlen, H., da Silva, M.R.R., Thomas, R., Soares, D.R.
& Olivier, P. (2007): Nb–Ta–(Ti–Sn)- oxide mineral
chemistry as tracers of rare-element granitic pegmatite
fractionation in the Borborema Province, northeast Brazil.
Mineral. Deposita 42, (in press).
Beurlen, H., Soares, D.R., Prado-Borges, L.E., Leo, H.S.V.
& Da Silva, M.R.R. (2003a): Análise de mecanismos de
substituição em tantalato exótico: provável titano-ixiolita
na Província Pegmatítica da Borborema. Rev. Geologia
(UFCE) 16, 7-18.
Beurlen, H., Soares, D.R., Thomas, R., Prado-Borges, L.E.
& Castro, C. (2005a): Mineral chemistry of tantalate spe-
cies new in the Borborema Pegmatitic Province, northeast
Brazil. An. Acad. Bras. Ciênc. 77, 169-182.
Beurlen, H., Thomas, R., Barreto, S.B. & Da Silva, M.R.R.
(2003b): Nova ocorrência de ferrowodginita em asso-
ciação com cassiterita, strüverita e tapiolita na Província
Pegmatítica da Borborema, nordeste do Brasil. Est. Geol.
13, 35-45.
Brasil (1998): Mapa Geológico do Estado do Rio Grande do
Norte. Brasil, DNPM-CPRM/UFRN.
Brasil (2002): Mapa Geológico do Estado da Paraíba. Brasil,
DNPM-CPRM/CDRM.
Cameron, E.M., Jahns, R.H., McNair, H. & Page, L.R.
(1949): Internal structure of granitic pegmatites. Econ.
Geol., Monogr. 2, 1-115.
Černý, P. (1989a): Characteristics of pegmatite deposits
of tantalum. In Lantanides, Tantalum, and Niobium (P.
Möller, P. Černý & F. Saupé, eds.). Springer, Heidelberg,
Germany (195-235).
Černý, P. (1989b): Exploration strategy and methods for peg-
matite deposits of tantalum. In Lantanides, Tantalum, and
Niobium (P. Möller, P. Černý & F. Saupé, eds.). Springer,
Heidelberg, Germany (274-302).
Černý, P. (1991): Rare element granitic pegmatites. 1. Anat-
omy and internal evolution of pegmatite deposits. Geosci.
Can. 18, 49-67.
Černý, P. (1992): Geochemical and petrogenetic features of
mineralization in rare-element granitic pegmatites in the
light of current research. Appl. Geochem. 7, 393-416.
Černý, P. & Ercit, T.S. (1989): Mineralogy of niobium and
tantalum: crystal chemical relationships, paragenetic
adspects and their implications. In Lantanides, Tantalum,
and Niobium (P. Möller, P. Černý & F. Saupé, eds.).
Springer, Heidelberg, Germany (27-79).
Černý, P. & Ercit, T.S. (2005): The classification of granitic
pegmatites revisited. Can. Mineral. 43, 2005-2026.
Černý, P., Ercit, T.S., Wise, M.A., Chapman, R. & Buck,
H.M. (1998): Compositional structural and phase relation-
ships in titanian ixiolite and titanian columbite–tantalite.
Can. Mineral. 36, 547-561.
Černý, P., Masau, M., Goad, B.E. & Ferreira, K. (2005):
The Greer Lake leucogranite, Manitoba, and the origin
of lepidolite-subtype granitic pegmatites. Lithos 80,
305-321.
Černý, P. & Němec, D. (1995): Pristine vs. contaminated
trends in Nb,Ta-oxide minerals of the Jihlava pegmatite
district, Czech Republic. Mineral. Petrol. 55, 117-129.
Černý, P., Paul, B.J. Hawthorne, F.C. & Chapman, R.
(1981): A niobian rutile – disordered columbite inter-
growth from the Huron Claim pegmatite, southeastern
Manitoba. Can. Mineral. 19, 541-548.
Cunha e Silva, J. (1981): Formação polimetalífera da região
da Borborema, Estados do Rio Grande do Norte e Paraíba.
Companhia Pesquisa Recursos Minerais, Recife, Unpubl.
Rep.
1386 the canadian mineralogist
Cunha e Silva, J. (1983): Zonação polimetalífera da Região
da Borborema, Estado do Rio Grande do Norte e Paraíba.
Mineração e Metalurgia 47(445), 24-36.
Da Silva, M.R.R. (1993): Petrographical and Geochemical
Investigations of Pegmatites in the Borborema Pegmatitic
Province of Northeastern Brasil. Ph.D. thesis, Ludwigs
Maximillian Univ., Munich, Germany.
Da Silva, M.R.R., Höll, R. & Beurlen, H. (1995): Bor-
borema Pegmatitic Province: geological and geochemical
characteristics. J. S. Am. Earth Sci. 8, 355-364.
Da Silva, M.R.R. & Silva, D. (2006): Manganocolumbite
and cassiterite exsolution lamellae in ilmenite from the
Pitombeiras pegmatite (Acarí – Rio Grande do Norte) in
the Borborema Pegmatitic Province, NE-Brazil. Est. Geol.
16(2), 3-15.
Droop, G.T.R. (1987): A general equation for estimating Fe3+
concentrations in ferromagnesian silicates and oxides from
microprobe analyses using stoichiometric criteria. Mineral.
Mag. 51, 431-435.
Ebert, H. (1969): Geologia do Alto Seridó. Recife, Brazil.
SUDENE Serie Geol. Reg. 11.
Ebert, H. (1970): The Precambrian geology of the “Bor-
borema” belt (states of Paraíba and Rio Grande do Norte)
and the origin of its mineral provinces. Geol. Rundsch.
59, 1294-1327.
Ercit, T.S., Černý, P. & Hawthorne, F.C. (1992b): The
wodginite group. III. Classification and new species. Can.
Mineral. 30, 633-638.
Ercit, T.S., Černý, P., Hawthorne, F.C. & McCammon, C.A.
(1992a): The wodginite group. II. Crystal chemistry. Can.
Mineral. 30, 613-631.
Groat, L.E., Putnis, A., Kissin, S.A., Ercit, T.S., Haw-
thorne, F.C. & Gaines, R.V. (1994): Staringite discred-
ited. Mineral. Mag. 58, 271-277.
Jardim de Sá, E.F. (1994): A Faixa Seridó (Província Bor-
borema, NE do Brasil) e seu significado geodinâmico
na cadeia Brasiliana/Panafricana. Ph.D. thesis, Univ. of
Brasília, Brasília, Brazil.
Jardim de Sá, E.F., Legrand, J.M., Galindo, A.C. & Hack-
spacker, P.C. (1986): Granitogênese Brasiliana no Seridó:
o maciço de Acari (RN). Rev. Bras. Geoc. 16, 95-105.
Jardim de Sá, E.F., Legrand, J.M. & McReath, I. (1981):
Estratigrafia de rochas granitóides na região do Seridó
(RN–PB) com base em critérios estruturais. Rev. Bras.
Geoc. 11, 50-57.
Johnston, W.D., Jr. (1945): Beryl–tantalite pegmatites of
northeastern Brazil. Geol. Soc. Am., Bull. 56, 1015-1070.
Klementová, M. & Rieder, M. (2004): Exsolution in niobian
rutile from the pegmatite at Greenbushes, Australia. Can.
Mineral. 42, 1859-1870.
Legrand, J.M., Deutsch, S. & Souza, L.C. (1991): Datação
U/Pb e granitogênese do maciço Acari (RN). In 14o Simp.
Geol. Nordeste, SBG (Recife). Atas, Bol. 12,172-174.
Lima, E.S. (1986): Metamorphism and Tectonic Evolution in
the Seridó Region, Northeastern Brazil. Ph.D. thesis, Univ.
of California at Los Angeles, Los Angeles, California.
Martin, R.F. & De Vito, C. (2005): The patterns of enrich-
ment in felsic pegmatites ultimately depend on tectonic
setting. Can. Mineral. 43 2027-2048
Neiva, A.M.R. (1996): Geochemistry of cassiterite and its
inclusions and exsolution products from tin and tungsten
deposits in Portugal. Can. Mineral. 34, 745-768.
Ramdohr, P. (1969): The Ore Minerals And Their Inter-
growths. Pergamon, London, U.K.
Rolff, P.M.A. (1946): Minerais dos pegmatitos da Borborema.
Departamento Nacional de Produção Mineral, Div. Fom.
Prod. Min. (DNPM–DFPM), Rio de Janeiro. DFPM Bol.
78, 23-76.
Roy, P.L., Dottin, O. & Madon, H.L. (1964): Estudo dos
pegmatitos do Rio Grande do Norte e da Paraíba. Super-
intendência de Desenvolvimento do Nordeste (SUDENE),
Série Geol. Econ. 1, 1-124.
Schneiderhöhn, H. (1961): Die Erzlagerstätten der Erde. 2.
Die Pegmatite. Jena, Germany.
Scorza, E.P. (1944): Província Pegmatítica da Borborema.
DNPM, Rio de Janeiro. Div. Geol. Min., Bol. 112, 1-57.
Smeds, S.-A., Černý, P. & Chapman, R. (1999): Niobian
calciotantite and plumboan-stannoan cesstibtantite from
the island of Utö, Stockholm Archipelago, Sweden. Can.
Mineral. 37, 665-672.
Soares, D. (2004): Contribuição à Petrologia de Pegmatitos
Mineralizados em Elementos Raros e Elbaítas Gemológi-
cas da Província Pegmatítica da Borborema, NE-Brasil.
Ph.D. thesis, Federal University of Pernambuco, UFPE,
Recife, Pernambuco, Brazil.
Soares, D.R. & Beurlen, H. (2003): Química mineral de
espessartitas da Província Pegmatítica da Borborema.
Ninth Congress Brasileiro Geoquímica, Extended Abstr.
Vol., 667-668.
Soares, D.R., Beurlen, H. & Ferreira, A.C.M. (2004):
Evolução composicional das turmalinas do pegmatito
Capoeira 2, Província Pegmatítica da Borborema, NE do
Brasil. Estudos Geológicos 14, 31-43.
Soares, D.R., Beurlen, H., Ferreira, A.C.M. & Da Silva,
M.R.R. (2007): Gahnite mineral chemistry and pegmatite
fractionation in the Borborema Province, northeast Brazil.
An. Acad. Bras. Ciên. 179(3), 1-10.
Tindle, A.G. & Breaks, F.W. (2000): Columbite–tantalite
mineral chemistry from rare element granitic pegmatites:
 titanian ixiolite – niobian rutile intergrowths, borborema, brazil 1387
Separation Lake area, NW Ontario, Canada. Mineral.
Petrol. 70, 165-198.
Tindle, A.G., Breaks, F.W. & Webb, P.C. (1998): Wodginite-
group minerals from the Separation Rapids rare-element
granitic pegmatite group, northwestern Ontario. Can.
Mineral. 36, 637-658.
Uher, P. & Broska, I. (1995): Pegmatites in two suites of
Variscan orogenic granitic rocks (western Carpathians,
Slovakia). Mineral. Petrol. 55, 27-36.
Uher, P., Černý, P., Chapman, R., Határ, J. & Miko, O.
(1998): Evolution of Nb,Ta-oxide minerals in the Prašivá
granitic pegmatites, Slovakia. I. Primary Fe,Ti-rich assem-
blage. Can. Mineral. 36, 525-534.
Van Schmus, W.R., Brito Neves, B.B., W illiams, I.S.,
H ackspacher , P.C., F etter , A.H., D antas , E.L. &
Babinski, M. (2003): The Seridó Group of NE Brazil, a
late Neoproterozoic pre- to syn-collisional basin in West
Gondwana: insights from SHRIMP U–Pb detrital zircon
ages and Sm–Nd crustal residence (TDM) ages. Precamb.
Res. 127, 287-327.
Varlamoff, N. (1959): Zonéographie des quelques champs
pegmatitiques de l’Afrique Centrale et les classifications
de K.A. Vlasov et de A.I. Guinsbourg. Ann. Soc. Géol.
Belg. 82, 55-87.
Vlasov, K.A. (1952): Texturelle und paragenetische Glie-
derung der Pegmatite. Mitt. Akad. Wiss. USSR, Geol. Ser.
2, 30-55.
Wirth, R. (2004): Focused ion beam (FIB): a novel technol-
ogy for advanced application of micro- and nanoanalysis
in geosciences and applied mineralogy. Eur. J. Mineral.
16, 863-876.
Wise, M.A., Černý, P. & Falster, A.U. (1998): Scandium
substitution in columbite-group minerals and ixiolite. Can.
Mineral. 36, 673-680.
Received July 13, 2006, revised manuscript accepted Novem-
ber 26, 2007.
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