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Tracing the chemical evolution of primary pyrochlore from plutonic to

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DOI: 10.1180/minmag.2012.076.2.07

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Mineralogical Magazine, April 2012, Vol. 76(2), pp. 377–392

Tracing the chemical evolution of primary pyrochlore from

plutonic to volcanic carbonatites: the role of fluorine

A. C. J. M. BAMBI1, A. COSTANZO2,*, A. O. GONÇALVES1 AND J. C. MELGAREJO3

1
Departamento de Geologia, Faculdade de Ciências, Universidade Agostinho Neto, Av. 4 de Fevereiro 7, 815
Luanda, Angola
2
Earth and Ocean Sciences, School of Natural Sciences National University of Ireland, Galway, University Road,
Galway, Ireland
3
Departament de Cristal·lografia, Mineralogı́a i Dipòsits Minerals, Universitat de Barcelona, c/Martı́ i Franquès
s/n, 08028 Barcelona, Catalonia, Spain
[Received 17 January 2011; Accepted 20 June 2011; Associate Editor: Frances Wall]

ABSTRACT

Three Angolan carbonatites were selected to evaluate the change in composition of pyrochlores during
magmatic evolution: the Tchivira carbonatites occur in a plutonic complex, the Bonga carbonatites
represent hypabyssal carbonatites and the Catanda carbonatites are volcanic in origin. In Tchivira
pyrochlore, zoning is poorly developed; fluorine is dominant at the Y site; chemical zoning may arise as
a result of substitutions for Nb in the B site; and the rare earth element (REE), U, Th and large-ion
lithophile element (LILE) contents are very low. Pyrochlores from Bonga show oscillatory zonation;
the F and Na contents are lower than those in the pyrochlores from Tchivira; and as substitution of Na
at the A site increases, the Th, U, REE contents and inferred vacancies also increase. Pyrochlores from
Catanda display complex textures. They generally have a rounded corroded core, which is mantled by
two or three later generations. The core composition is similar to the Bonga pyrochlores. The rims are
enriched in Zr, Ta, Th, Ce and U, but depleted in F and Na. In pyrochlores from the Angolan
carbonatites, the F and Na contents decrease from plutonic to volcanic settings and there is enrichment
of Th, U and REE in the A site and Ta and Zr in the B site. Zoning may be explained by changes in the
activity of F, due to the crystallization of fluorite or apatite in the plutonic and hypabyssal carbonatites,
or to volatile exsolution in the volcanic carbonatites.

K EY WORDS : Angola, carbonatite, zonation in pyrochlore, fluorine, high field strength elements, HFSE,
pyrochlore, rare earth elements, REE, mineral zonation.

Introduction (Mariano, 1989b). The presence of Nb minerals

CARBONATITES and other genetically related alka-
line rocks display characteristic geochemical
enrichments in rare earth elements (REEs), Ba,
Nb, Sr, Ta, Th, U, Zr, V and Ti (Mariano, 1989a;
Woolley and Kempe, 1989). Apatite magnetite
mineralization is associated with the early stages
of carbonatite activity and carbonatites are
commonly rich in Nb, which is commonly
present in minerals of the pyrochlore group
* E-mail: alessandra.costanzo@nuigalway.ie
DOI: 10.1180/minmag.2012.076.2.07
or enrichment in Nb is a good criterion for
carbonatite identification. Niobium is usually
concentrated in intermediate pulses of carbonatite
activity (Kapustin, 1980).
Pyrochlore-group mineral concentrates are
produced mainly from carbonatites. They are
found in nearly all carbonatite types, at least in
accessory amounts. Their chemical composition is
widely variable, typically containing essential
amounts of Nb, Ta or Ti. The general formula is
A2 mB2X6 wY1 n·pH2O, where A = Na, Ca, Mn,
Fe2+, Sc, Sn, Sr, Sb, Cs, Ba, REE, Pb, Bi, Th and
U; B = Nb, Ta, Ti, Al, Fe3+, Zr, Sn and W; X = O,

# 2012 The Mineralogical Society

 A. C. J. M. BAMBI ET AL.
OH; and Y = O, OH, and F. Three pyrochlore
subgroups were defined by Hogarth (1977) on the
basis of the major B-site cations: pyrochlore (with
Nb + Ta > 2Ti; Nb > Ta), microlite (with Nb + Ta
> 2Ti; Ta 5 Nb), and betafite (with 2Ti 5 Nb +
Ta). Individual mineral species within each group
were defined by the cations present at the A site.
Atencio et al. (2010) proposed a new nomen-
clature, which is accepted by the International
Mineralogical Association (IMA). Pyrochlore-
group minerals are classified on the basis of the
dominant elements at the A, B and Y sites,
following the IMA’s 50% rule.
For a long time pyrochlore has been proposed
as a possible natural analogue for nuclear waste
recipients (Lumpkin and Ewing, 1985) and for
this reason, there is great interest in understanding
elemental behaviour in the pyrochlore structure,
in particular, high field strength elements (HFSE)
and REEs.
The composition of pyrochlore-group minerals
in carbonatites is commonly variable due to the
presence of two or more generations, to the
subsolidus replacement of early pyrochlore and to
the supergene alteration of the outer rims of
crystals (Petruk and Owens, 1975; Kapustin,
1980; Wall et al., 1996; Williams et al., 1997;
Chakhmouradian and Mitchell, 1998; Hogarth et
al., 2000; Nasraoui and Bilal, 2000; Zurevinski
and Mitchell, 2004; Lee et al., 2006). The
variation in Ta content can show two different
trends: either Ta enrichment from the core to the
crystal rim or the opposite (Kjarsgaard and
Mitchell, 2008). The reason for these trends is
unclear, but F activity in the magma may be a key
factor (Kjarsgaard and Mitchell, 2008). Mitchell
and Kjarsgaard, (2004) showed that F-rich magma
is critical in stabilizing pyrochlore-group minerals
in preference to other Nb-bearing minerals, such
as perovskites, in carbonatites. Perovskite-group
minerals tend to crystallize in water-rich magmas.
The Angolan F-rich carbonatite complexes
described in this study are emplaced at different
levels in the crust and provide a unique
opportunity to compare variations in pyrochlore
composition from plutonic to volcanic environ-
ments. The Tchivira carbonatites are plutonic, the
Bonga carbonatites are subvolcanic and the
Catanda carbonatites are effusive.
Analytical methods
The internal structure of the pyrochlores, prepared
as thin sections and polished blocks, was studied
378
using back-scattered electron imaging (BSE) on a
scanning electron microscope (SEM). The images
were used to select appropriate points for
qualitative analysis using energy dispersive
X-ray spectrometry (EDS). The EDS analyses
were performed at the Serveis Cientı́fico-Tècnics,
Universitat de Barcelona on a Quanta Q-200 (FEI
Company) scanning electron microscope
equipped with a Genesis energy-dispersive micro-
analysis system and on a Cambridge Instruments
Stereoscan 360 scanning electron microscope
equipped with an INCA ENERGY 200 micro-
analysis system. Operating conditions were 30 kV
accelerating voltage with a 1 nA beam current and
a 20 25 mm sample-to-detector distance.
Quantitative major-element analyses, using an
electron microprobe (EPMA) with wavelength-
dispersive spectrometry (WDS), were carried out
at the Serveis Cientı́fico-Tècnics of the
Universitat de Barcelona and at the Natural
History Museum in London. Wavelength-disper-
sive analyses, performed using a Cameca SX50
electron microprobe, used the PAP matrix
correction programme (Pichou and Pichoir,
1984). The operating conditions were chosen to
minimize devolatilization: an accelerating voltage
of 15 20 kV was combined with a beam current
of 5 20 nA and a 10 15 mm spot diameter.
Standards and lines used for the analyses were:
fluorite (FKa); albite (NaKa); periclase (MgKa);
synthetic Al2O3 (AlKa); diopside (SiKa); ortho-
clase (KKa); wollastonite (CaKa); rutile (TiKa);
rhodonite (MnKa); Fe2O3 (FeKa); celestine
(SrLa); YAG (YLa); ZrO (ZrLa); Nb (NbLa);
SnO (SnLa); baryte (BaLa); LaB6 (LaLa); CeO2
(CeLa); REE1 (PrLb); REE4 (NdLa); REE3
(SmLa); Ta (TaMa); W (WMa); PbS (PbMa);
ThO2 (ThMa); UO2 (UMa).
Geological setting
Africa is the continent most richly endowed with
alkaline rocks and carbonatites (Woolley, 2001);
it has about 40% of the known world carbonatite
occurrences according to Woolley (1989). One of
the 18 major swells associated with carbonatites
in Africa (Le Bas, 1971) extends into Angola
where the majority of carbonatites crop out along
the Lucapa structure (Lapido-Loureiro, 1968,
1973). The Lucapa structure is a northeast–
southwest trending rift system that formed in the
early Cretaceous (138 130 Ma) (Issa Filho et al.,
1991). The carbonatites and associated alkaline
rocks belong to the Paraná Angola Etendeka
 F IN CARBONATITIC PYROCHLORE

Province and occur as ring complexes and other
central-type intrusions (Lapido-Loureiro, 1968,
1973) along northeast–southwest trending
tectonic lineaments, parallel to the trend of
coeval Namibian alkaline complexes (Alberti et
al., 1999). Most of the Angolan carbonatite–
alkaline bodies are located along the atypical part
of the Moçamedes Arch, a structure which is the
African counterpart of the Ponta Grossa Arch in
southern Brazil, where there are several further
alkaline carbonatite complexes of early
Cretaceous age (Coltorti et al., 1993; Alberti et
al., 1999).
The central Angolan carbonatites and alkaline
complexes intrude a crystalline Precambrian
basement (Carvalho, 1983), which forms part of
the southern unit of the central African mega-unit,
made up of the Congo, Kasai and Angolan cratons
(Goodwin, 1996). The carbonatite complexes
intrude Precambrian granite, gneiss and migmatite
hosted by the Angola Namibia gabbro-anortho-
site complex (Issa Filho et al., 1991) (Fig. 1).
In Angola, carbonatites occur in three main
areas (Issa Filho et al., 1991): (1) the central–
western area (Catanda); (2) the central area
(Monte Verde to Sulima, Baliundo, Coola,
Longonjo, Tchivira Bonga); and (3) the south-
western area, close to the Namibian border
(Virulundo, Lupongola). Three different morpho-
logical and lithological types of carbonatite have
been distinguished: (1) truncated cones of unusual
relief, with a large volume of carbonatites and
abundant feldspathic carbonatite breccias in the
exocontacts (i.e. Bonga, Virulundo, Bailundo,
Longonjo); (2) carbonatitic ring-dykes, intruded
into syenites, nepheline syenites and ijolites (as at
Tchivira); (3) pyroclastic sequences constituting
small hills (as at Catanda).
The alkaline carbonatite occurrences at Mount
Tchivira and Mount Bonga are among the largest
of the Angolan complexes (Coltorti et al., 1993).
Tchivira Bonga is a polygenetic complex that
consists of two major intrusions in a Proterozoic
granitic basement. Their proximity suggests that
the two bodies are the expression of a common
magmatic event that took place in two distinct
conduits at shallow depth. Remnants of carbona-
titic volcanic edifices are found near Catanda in

FIG. 1. Geological map of Angola showing the location of the alkaline and carbonatite complexes and sample
localities (Modified after de Carvalho et al., 2000).

379
 A. C. J. M. BAMBI ET AL.

the Cuanza Sul province, about 400 km southeast of the accessory minerals. Calcite is the most
of Luanda and occupy an area of about 30 km2. common carbonate; it occurs as anhedral mm-
The main Tchivira plutonic centre consists of
early rings of ijolite and nepheline syenite with an
inner carbonatitic ring (Matos Alves, 1968). Late
alkaline gabbroic to syenitic intrusions partially
disrupt earlier structures on the western side. The
carbonatites form annular structures which cross-
cut gabbros, ijolites, nepheline syenites and
syenites. They are made up of calciocarbonatites
and late-stage magnesiocarbonatites, which
display marked topographic relief (Fig. 2a).
Late-stage hydrothermal events have produced
widespread replacement of carbonatite mineral
associations by mineral assemblages including
quartz, fluorite, baryte, ankerite and dolomite
(Bambi et al., 2004).
The Bonga complex, which lies northeast of
Tchivira, is a truncated carbonatite plug which
rises to altitudes of up to 800 m above the local
basement (Fig. 2b) and is surrounded by fenite–
carbonatitic breccias. It is a concentric structure
with massive calcite carbonatites at the centre
(partly replaced by ankerite carbonatites)
surrounded by concentric carbonatite ring-dykes
up to 15 m wide. This ensemble is cross-cut by
alnöite pipes. The massif probably represents an
exhumed subvolcanic environment, as suggested
by the extensive development of carbonatite
breccias. Carbonatites from the Bonga complex
contain approximately 800 Mt of niobium ore at
0.5% Nb2O5; their phosphate content reaches 10%
P2O5 (Terraconsult, 1983).
The Catanda volcanic structure consists mainly
of sequences of pyroclastic carbonatites with
minor interbedded carbonatitic lavas (Silva and
Pereira, 1973). The pyroclastic rocks are
primarily lapilli beds, although coarser units are
present locally (Fig. 2c).

Mineralogy of the carbonatites

The mineral assemblages at Tchivira and Bonga
are quite similar in composition and texture and
consist mainly of carbonates including calcite,
dolomite and ankerite. Apatite, magnetite and
phlogopite are common accessory minerals and
pyrochlore is abundant in some bands. Other
minerals that occur in minor amounts include
strontianite, REE-bearing carbonates (mainly
synchysite-(Ce)), Ca-REE fluorocarbonates and
baryte. Most of the carbonatite outcrops described
in this study display centimetre-scale to milli-
metre-scale banding produced by the distribution
FIG. 2. Angolan carbonatite localities. (a) A panoramic
view of the left margin of the Tchivira structure. Part of
the carbonatite ring-dyke crops out in the foreground;
Mount Tchivira, which is composed of nepheline
syenite, is in the background. (b) A panoramic view of
the Bonga plug from the south. (c) A detailed view of
the pyroclastic beds at the eastern end of the Catanda
structure.

380
 F IN CARBONATITIC PYROCHLORE
sized grains. Apatite occurs as subhedral pris-
matic crystals up to 5 mm in length either
disseminated through the rock mass or concen-
trated in millimetre-scale bands. Phlogopite is
present as subhedral tabular crystals up to 2 mm
across. Magnetite is most commonly found as
euhedral crystals up to 10 mm on edge, it also
occurs as massive bodies up to several metres in
thickness. Most of the primary magmatic associa-
tions have been strongly altered and replaced by
subsolidus hydrothermal minerals including
fluorite, quartz and hydrothermal calcite, dolomite
and ankerite. An early fine-grained generation of
these minerals occurs as irregular replacements in
the carbonatites. Several later generations fill
fractures where they occur as larger euhedral
crystals. The Ca-REE fluorocarbonates which are
found in all the carbonatites are products of late-
stage hydrothermal processes. They occur mainly
as interstitial material and fracture fillings, often
associated with ankerite transformation products,
and also as small radiating fibrous spheroidal
bodies in the carbonates.
The pyroclastic carbonatites are composed of a
mixture of xenoliths in a calcite matrix. The
xenoliths include carbonatite fragments, basalt,
fenitized granite, and mantle rock. Carbonatite
lavas have a fine-grained calcite matrix and
contain centimetre-sized euhedral pyroxene,
micas, olivine, amphibole and apatite pheno-
crysts. Some of the carbonatite lavas have a
trachytic texture which is produced by the
complete replacement of platy crystals by
secondary calcite. These have been interpreted
as strongly weathered natrocarbonatites (Bambi et
al., 2008). Other accessory minerals occur in the
fine-grained matrix and include minor fine-
grained pyrochlore and zoned magnetite–
ulvöspinel crystals. Baddeleyite is quite common
and is found as small inclusions in the spinels or
scattered in the matrix; zirconolite, zircon and
chromite are rare.
Pyrochlore
Pyrochlore is by far the most abundant Nb-bearing
mineral in carbonatitic associations and has been
found at all of the Angolan complexes in
accessory amounts. It is most abundant in the
outer carbonatite ring-dykes of the subvolcanic
Bonga complex and the occurs in the smallest
amounts in the effusive carbonatites from Catanda.
Pyrochlore is found in colluvial sediments close to
the carbonatite massifs and is dispersed in the
381
alluvial sediments of the surrounding fluvial
network. Complex replacement along grain
discontinuities and metamictic alterations have
been observed within and surrounding the crystals.
These are produced by subsolidus processes
during late-stage hydrothermal or supergene
alteration, and are not described here.
Pyrochlore crystals from Tchivira typically
occur as euhedral octahedra {111} with plane
faces. They have a relatively simple internal
structure and are either homogeneous or have
simple compositional zoning, with a homoge-
neous rounded core mantled by a relatively
homogeneous border zone. The crystals are
typically less than 50 mm across (Fig. 3a,b) and
most have been affected by subsolidus replace-
ment processes.
Pyrochlore from the different units at Bonga
tends to be euhedral; the crystals are commonly
intergrown with other minerals, particularly
apatite, which is particularly abundant in the
outer zones of the crystals in some cases (Fig. 3c).
Most of the crystals show concentric oscillatory
zoning when examined in thin section or by BSE
imaging (Fig. 3d). The zones are sharp, indicating
a primary origin, and therefore the crystals were
selected to investigate primary magmatic zoning.
Crystals from the brecciated zones of the Bonga
carbonatite are commonly fractured. They are
variable in size, reaching as much as 5 mm, the
largest being found in the outer carbonatite ring-
dykes. Subsolidus replacements are commonly
developed on the Bonga pyrochlores.
Pyrochlore from the extrusive carbonatites at
Catanda is very small (<50 mm; Fig. 3e) and it has
a much simpler internal structure, which usually
consists of a homogeneous irregular and smooth
corroded core mantled by thin rims of different
compositions. The outermost rim tends to be
euhedral. Many of these crystals also display
evidence of micro-brecciation produced by
explosive volcanic processes. There are no later
generations of pyrochlore rimming the broken
crystals, indicating that zoning was produced in a
magma chamber prior to eruption (Fig. 3f). The
Catanda pyrochlore is unaffected by subsolidus
processes.
Mineral chemistry of primary pyrochlore
About 60 pyrochlore crystals from 30 samples
collected from the three Angolan localities
described in the previous sections were analysed
to investigate the variations in pyrochlore
A. C. J. M. BAMBI ET AL.

382
 F IN CARBONATITIC PYROCHLORE

composition at different emplacement levels.
Compositions of pyrochlore crystals from
Tchivira, Bonga and Catanda are listed in
Table 1.
Niobium is the dominant substituent at the B
site in most of the crystals from all these
environments; all of the samples are members of
the pyrochlore group in the classification of
Atencio et al. (2010) (Fig. 4a). The A site is
mostly occupied by Ca, although Na is dominant
in some analyses from Tchivira (Fig. 4b).
Fluorine is the dominant Y-site anion in the
Tchivira and Bonga samples, whereas OH is
dominant in some pyrochlore from Catanda. In
the nomenclature developed by Atencio et al.
(2010), the Tchivira crystals are fluornatropyro-
chlore and fluorcalciopyrochlore, the Bonga
crystals are fluorcalciopyrochlore and those from
Catanda are hydroxycalciopyrochlore.
Primary pyrochlore from Tchivira has a narrow
compositional range. Zoning is due to small
changes in the substituents at the A and B sites.
There is near-complete occupancy of the A site by
Na and Ca, and the number of vacancies at this
site is the lowest of all the studied samples. The
crystals contain very small amounts of Th, U and
REEs. A small increase in Th content at the A site,
which correlates with an enrichment of Ti at the B
site, may account for the zoning observed. The F
content is remarkably constant within the crystal
(with a mean value close to 1 apfu); F is dominant
at the Y site.
Primary pyrochlore from Bonga has relatively
small compositional variations, although crystals
from the different units display oscillatory zoning.
The mean Nb2O5 content is 62.41 wt.% (with a
standard deviation of 6.37). The oscillatory zoning
in the crystals reflects small changes in cation
proportions at the B site, the most important of
which are in the Nb:(Nb + Ti) ratio. Tantalum
contents are generally low (with a mean value of
0.81 wt.% Ta2O5 and a standard deviation of 1.08)
and correlate positively with Zr content. There are
minor variations in substituents at the A site, where
the Th content correlates with Ta and Zr contents.
Fluorine does not completely occupy the Y site,
and this suggests an elevated hydroxyl content.
Primary pyrochlores from the pyroclastic flows
and lavas at Catanda have a wider range of
composition than those from the intrusive
complexes. The rounded cores of crystals have
higher Ta contents than their intrusive equivalents
(up to 4 wt.% Ta2O5). The B sites in the crystal
rims are more enriched either in Ta (up to 6.35
wt.% Ta2O5) or Zr (up to 9.88 wt.% ZrO2),
whereas the A sites are strongly enriched either in
Ce (up to 8.17 wt.% Ce2O3), Th (up to 8.75 wt.%
ThO2), or U (up to 12.72 wt.% UO2). The F
content is highly variable in different zones
(0.70 4.84 wt.% F), but it is very low in
comparison with the pyrochlores in the intrusive
rocks.
Discussion
The variations in pyrochlore composition are
considered both at a microscopic level and in a
geological context in the discussion that follows.
Crystal zoning in pyrochlore has been reported in
all known carbonatites, including oceanic carbo-
natites (Hodgson and Le Bas, 1992). In the
Angolan carbonatites, the variations are not
particularly remarkable in the intrusive facies,
but they are more significant in the volcanic
rocks. The largest changes in the chemical
composition of the pyrochlores are observed
from plutonic to hypabyssal and to volcanic. In
the paragraphs that follow, variations in the

FIG. 3 (facing page). Textural patterns of pyrochlores in Angolan carbonatites under the scanning electron
microscope in BSE mode. (a) Representative texture of the Tchivira carbonatite showing euhedral pyrochlore (pcl)
in a groundmass mainly composed by calcite (cc) and dolomite (dol), with magnetite (mag) as accessory mineral.
The small white dots are hydrothermal baryte and synchysite. (b) Detail of the internal texture of a typical pyrochlore
crystal from Tchivira. Note the strong replacement of the primary pyrochlore (Ppcl) by late-stage secondary
hydrothermal pyrochlore (Spcl), and the occurrence of late hydrothermal quartz (qtz) in association with calcite and
dolomite. (c) Typical primary pyrochlore (Ppy) from the Bonga carbonatite. The pyrochlore is intergrowth with
apatite (ap) and calcite; magnetite is also present in the groundmass. (d) Detail of the internal texture of a pyrochlore
crystal from Bonga carbonatites. Concentric zoning is seen on the primary pyrochlore and this zoning is cross-cut by
late-stage hydrothermal pyrochlore. (e) Primary pyrochlore crystal in a pyroclastic carbonatite. Crystals of calcite,
apatite and spinel (spl) are present in calcite cement. (f) Zoned pyrochlore crystal from the Catanda volcanics. The
external bright rim of the crystal is due to a strong enrichment in heavy elements. Note the brecciation cross-cutting
the zoning.

383
 TABLE 1. Chemical composition of representative pyrochlore crystals from the Tchivira, Bonga and Catanda complexes. The atoms per formula unit are
calculated based on 2 a.p.f.u. in the B site; it is assumed OH+F=1 a.p.f.u.

Locality ——— Tchivira (plutonic) ——— ——— Bonga (hypabyssal) ——— ——— Catanda (volcanic) ———
—— Rim —— —— Core —— —— Rim —— —— Core —— —— Rim —— —— Core ——

No. T-27-7 T-27-10 T-27-1 T-27-2 B-7c-47 B-7c-44 B-7c-11 B-7c-12 Cat-79-7 Cat-79-11 Cat-79-15 Cat-79-16

Na2O 7.63 8.42 7.64 7.36 4.81 4.99 5.82 5.23 1.87 2.09 6.51 6.73
CaO 15.11 13.65 13.36 13.53 16.23 16.66 15.99 15.96 14.75 14.50 16.33 16.55
MnO 0.01 0.03 0.00 0.09 0.20 0.08 0.15 0.17 0.53 0.46 0.09 0.07
SrO 1.21 1.21 0.54 0.46 0.17 0.14 0.51 0.51 0.00 0.00 0.85 0.84
La2O3 0.36 0.19 0.29 0.25 0.43 0.29 0.33 0.21 0.62 0.49 0.14 0.14
Ce2O3 0.27 0.63 1.55 1.48 1.90 1.79 1.90 1.91 3.16 2.23 0.61 0.70
Nd2O3 0.12 0.29 0.46 0.63 1.12 0.88 0.22 0.21
PbO 0.22 0.40 0.19 0.36
ThO2 0.00 0.07 3.43 3.29 4.46 4.02 1.88 2.29 9.15 8.52 0.29 0.19
UO2 0.02 0.16 0.22 0.00 4.53 6.85 0.00 0.00
SiO2 0.35 0.33 0.12 0.27 0.00 0.00 0.17 0.18
TiO2 2.09 1.88 3.42 3.35 2.87 2.82 3.12 3.08 0.56 1.12 3.20 3.03
Fe2O3 0.15 0.04 0.43 0.45 0.72 0.81 0.61 0.66 1.34 1.68 0.17 0.22

384
ZrO2 0.00 0.04 1.46 1.51 2.11 2.32 2.03 2.25 7.15 8.49 1.50 0.59
Nb2O5 70.16 70.13 64.31 63.75 62.17 62.73 65.24 64.30 50.36 45.84 67.24 67.81
Ta2O5 0.05 0.05 0.05 0.26 0.96 0.26 0.26 0.06 2.62 4.83 0.13 0.00
F 5.00 5.17 4.99 4.94 3.70 3.33 4.13 4.10 0.74 0.76 4.59 4.38
A. C. J. M. BAMBI ET AL.

H2O(calc) 0.16 0.07 0.09 0.11 0.65 0.84 0.54 0.53 1.78 1.76 0.36 0.44
Sum 102.74 102.86 102.36 101.73 101.62 101.47 102.70 101.62 100.28 100.50 102.34 102.08
O=F 2.11 2.18 2.10 2.08 1.56 1.40 1.74 1.73 0.31 0.32 1.93 1.84
Total 100.64 100.68 100.26 99.65 100.06 100.07 100.96 99.90 99.96 100.18 100.41 100.23

A site
Na 0.876 0.970 0.903 0.871 0.582 0.599 0.676 0.615 0.255 0.287 0.745 0.777
Ca 0.962 0.869 0.872 0.885 1.084 1.106 1.027 1.036 1.113 1.099 1.033 1.056
Mn 0.001 0.002 0.000 0.005 0.011 0.004 0.008 0.009 0.032 0.028 0.005 0.004
Sr 0.042 0.042 0.019 0.016 0.006 0.005 0.018 0.018 0.000 0.000 0.029 0.029
La 0.008 0.004 0.007 0.006 0.010 0.007 0.007 0.005 0.016 0.013 0.003 0.003
Ce 0.006 0.014 0.035 0.033 0.043 0.041 0.042 0.042 0.081 0.058 0.013 0.015
Nd 0.003 0.006 0.010 0.014 0.028 0.022 0.005 0.004
Pb 0.004 0.007 0.003 0.006
Th 0.000 0.001 0.048 0.046 0.063 0.057 0.026 0.032 0.147 0.137 0.003 0.003
U 0.000 0.002 0.003 0.000 0.071 0.108 0.000 0.000
 F IN CARBONATITIC PYROCHLORE

1.892 elemental composition at each structural site and

0.108

0.011
0.136
0.010
0.017
1.826
0.000
2.000
0.825
0.175
the influence of F are considered.
The Na:Ca ratio at the A site in the Angolan
carbonatites is typically <1, except for some
pyrochlore crystal cores from Tchivira. Together
1.836
0.164

0.010
0.142
0.008
0.043
1.795
0.002
2.000
0.857
0.143
with the apparent lack of lueshite (NaNbO3) in the
Tchivira and Bonga carbonatites, this suggests a
low aNa:aCa ratio in the parental magma
(Lumpkin and Ewing, 1995). A general enrich-
1.751
0.249

0.000
0.060
0.089
0.293
1.465
0.093
2.000
0.170
0.830
ment trend in REEs is observed from the intrusive
to the extrusive carbonatites, but the behaviour of
REEs in the intrusive rocks is more complex. The
pyrochlores are enriched in LREE, particularly Ce
1.744
0.256

0.000
0.030
0.071
0.246
1.604
0.050
2.000
0.165
0.835

and the highest REE contents are found in the

crystal rims. There is very little data about the
behaviour of REE in carbonatite pyrochlores
worldwide. Cerium-rich pyrochlore replaces
1.763
0.237

0.141
0.030
0.067
1.762
0.001
2.000
0.786
0.214

latrappite ((Ca,Na)(Nb,Ti,Fe)O3) crystals in the

Oka carbonatite (Chakhmouradian, 1996), and a
slight increase in the total REE content from
centre to rim has been described in Namibian
1.807
0.193

0.141
0.028
0.059
1.768
0.004
2.000
0.783
0.217

carbonatites (Thompson et al., 2002).

The radioactive element contents of the
pyrochlores are not particularly high in most of
the analysed samples, particularly if they are
1.824
0.176

0.131
0.038
0.070
1.757
0.004
2.000
0.652
0.348

compared with carbonatites worldwide. Uranium-

rich pyrochlores, ‘uranpyrochlore’ or ‘hatchetto-
lite’, have been described as primary phases in
many carbonatites worldwide (Williams, 1996)
1.803
0.127

0.135
0.034
0.064
1.751
0.016
2.000
0.729
0.271

and large amounts of U are found in many

pyrochlore crystals originating in carbonatites
(e.g. up to 22.92 wt.% UO2 in Newania, India;
Viladkar and Ghose, 2002; up to 23.6 wt.% UO2
1.876
0.124

0.006
0.154
0.021
0.045
1.760
0.004
2.000
0.954
0.046

in Delitzsch, Germany; Seifert et al., 2000) and

from kimberlites (up to 7.29 wt.%, Zurevinsky
and Mitchell, 2004). Hogarth and Horne (1989)
found uranium-rich pyrochlore (containing up to
1.896
0.104

0.007
0.157
0.020
0.043
1.772
0.001
2.000
0.962
0.038

26.6 wt.% UO2) in carbonatitic tuffs near Fort

Portal, Uganda. Thorium occurs in many carbo-
natites worldwide and crystals containing up to
29.62 wt.% ThO2 occur at the Afrikanda complex,
1.910
0.090

0.020
0.084
0.002
0.001
1.884
0.009
2.000
0.972
0.028

Kola peninsula, Russia (Chakhmouradian and

Zaitsev, 1999). The association between Th and
U is very erratic at the localities described above
and also in Angola. At the Angolan localities, U
1.897
0.103

0.021
0.093
0.007
0.000
1.879
0.001
2.000
0.937
0.063

and Th are concentrated in the crystal rims of

pyrochlores from the volcanic carbonatites.
The number of vacancies at the A site in the
pyrochlores tends to increase from plutonic to
hypabyssal environments in the Angolan carbo-
natites (Fig. 4b). Vacancies in the pyrochlore
OH (calc)
S cations

S cations
Vac. (A)

structure may be produced by several processes.

B site

Changes in the valence state of pyrochlores are

Nb
Ta
Fe
Zr
Ti
Si

complex due to the various substitutions that are

F

385
 A. C. J. M. BAMBI ET AL.

FIG. 4. Ternary plots of the chemical composition of pyrochlore crystals from the Angolan complexes: (a) in the
Na Ca-vacancies diagram of Kapustin (1980) and (b) in the Ti Nb Ta classification diagram of Hogarth et al.
(1977), adapted after Atencio et al. (2010).

possible at the A and B sites. The number of
vacancies has been attributed to selective leaching
of cations during weathering processes (e.g.
Lottermoser and England, 1988) but the presence
of radioactive elements must also be taken into
account as they can produce amorphization of the
structure and increase the number of vacancies
(e.g. Viladkar and Bismayer, 2010). In the case of
the analyses presented here, it is believed that this
latter mechanism is responsible for the variations
in the number of A-site vacancies in most cases,
because of the simultaneous changes of valences
at the A site (Th4+, U4+, REE3+ by Na+) and the B
site (Nb5+ and Ta5+ by Zr4+ and Si4+ and Fe3+).
Similar mechanisms have been proposed by other
researchers (e.g. Johan and Johan, 1994; Seifert et
al., 2000).
The amount of Ta in the Angolan carbonatites
is not particularly significant from an economic
point of view when compared with other
locations. Tantalum is an important element in
some carbonatite pyrochlores (Hogarth, 1989) and
reaches 26.9 wt.% Ta2O5 in the ‘uranpyrochlore’
described from an early calcite carbonatite at an
unidentified locality in eastern Siberia (Hogarth,
1989).
Variations in HFSE compositions have been
related to the stage of crystallization of the
carbonatite as well as the degree of differentiation
of carbonatite magma. Lee et al. (1999, 2006)
found a positive correlation between Ta and U in
carbonatites and phoscorites from Sokli, Finland,
and the highest concentrations were measured at
the pyrochlore crystal cores in early carbonatites.
Late carbonatites are depleted in these elements.
The U and Ta contents also decrease in dolomitic
carbonatites, whereas Th increases; however, the
opposite trend has been observed in the
Sallanlatvi carbonatite in the Kola Peninsula,
Russia (Zaitsev et al., 1999). Therefore, the
behaviour of HFSEs in carbonatites is highly
variable and cannot be attributed to only one
process.
In carbonatites, zirconium is commonly
concentrated in minerals such as baddeleyite and
zirconolite (Williams, 1996; Zaitsev et al., 1999);
high Zr contents have also been reported in
pyrochlores in carbonatites (Zurevinsky and
Mitchell, 2004) and kimberlites (up to
12.18 wt.% ZrO2, Sharygin et al., 2009). In the
latter, the lowest F values correlate with highest
Zr values. However, Zr values close to 0 wt.%
have also been found in the Lueshe carbonatites
(Nasraoui and Bilal, 2000).
Betafite is extremely rare in most carbonatites
worldwide (Hogarth, 1989); the betafite compo-
nent is very low in all the Angolan carbonatites
described here. Previously reported Ti contents in

386
 F IN CARBONATITIC PYROCHLORE
pyrochlore are generally less than 5 wt.% TiO2,
however values as high as 27.59 wt.% TiO2 were
reported from the Oka carbonatites by Zurevinsky
and Mitchell (2004).
Silicon in pyrochlore was considered to be
present as an impurity by Hogarth (1977), but
high SiO2 contents, which are negatively corre-
lated with Nb (up to 7.9 wt.% SiO2), have been
reported (Lumpkin and Mariano, 1996). Bonazzi
et al. (2006) suggested that only a small amount
of Si is incorporated in the pyrochlore structure,
and that it is mostly present in the radiation-
damaged parts of crystals. However, there is no
correlation between the Si and U + Th content in
the Angolan pyrochlores.
Compositions containing Fe at up to several
wt.% have been reported in some pyrochlore-
group minerals from carbonatites, the iron is
generally thought to be present as Fe3+ at the B
site, although Nasraoui and Waerenborgh (2001)
found significant amounts of Fe2+ in weathered
pyrochlores. In the analysed crystals Fe varies up
to 4.35 wt.% Fe2O3, therefore the ratio Fe3+:Fe2+
does not have a strong influence on the overall
charge balance.
The most significant changes in pyrochlore
composition are in the F and Na contents.
Fluorine tends to decrease from plutonic to
hypabyssal and extrusive carbonatites, and this
trend correlates with a decrease in Na at the A site
(Fig. 5a). The decrease in the F content can be
explained by co-crystallization of pyrochlore with
F-rich minerals such as fluorapatite. Fluorapatite
is more abundant at Bonga than Tchivira, and this
may explain the decrease of F in pyrochlore from
the Tchivira to the Bonga carbonatites. Fluorine-
dominant pyrochlore from Catanda only occurs in
the pyrochlore cores, which have similar F
contents to pyrochlore from Bonga. The rims of
crystals from Catanda contain very little F and
Na. This is believed to be related to the co-
crystallization of minerals such as fluorapatite,
which is very abundant in the matrix of the
carbonatite lavas, but might also be due to volatile
release from the magma before the pyrochlore had
crystallized completely.
Changes in the F (and Na) contents can also be
related to other changes at the A site. Reductions
in the F content are always associated with
simultaneous increases in REE contents (mainly
Ce, Fig. 5b) and HFSE contents including Th
(Fig. 5c) and U (Fig. 5d). To maintain charge
balance, increases in the HFSE and REE contents
also result in increased numbers of vacancies,
387
which may explain the decrease in Na in the A site
(Fig. 5e).
In contrast with the strong variations in Na and
the other A site elements, the Ca content is nearly
constant in pyrochlores from all the carbonatites,
with an average value of 1 apfu, although there is
a very slightly lower Ca content in the volcanic
carbonatites in comparison to the plutonic ones
(Fig. 5f). This suggests that the chemistry of the
carbonatite magma fixes the Ca content.
The changes at the B site are minor, but of
some interest. Niobium is the dominant substi-
tuent at the B site in all of the carbonatites. There
are significant correlations between F and some of
the minor substituent elements at this site. There
is a decrease in the amount of F, which parallels
the decrease in Nb, from plutonic to hypabyssal
and extrusive carbonatites (Fig. 6a). Tantalum
and zirconium have an opposite trend (Fig. 6b,c).
An impoverishment in Ti from plutonic to
volcanic carbonatites can be seen, although the
data are relatively erratic (Fig. 6d).
Fluorine is a key element in the development of
the different carbonatite magmas as it lowers the
corresponding melting and liquidus temperatures
(Jago and Gittins, 1991). A minimum of 1 wt.% F
is required in carbonatite magma for the crystal-
lization of pyrochlore in preference to other
Nb-bearing minerals (Jago and Gittins, 1993;
Mitchell and Kjarsgaard, 2004). Therefore, co-
crystallization of F-rich minerals may cause
extensive pyrochlore crystallization. This may
provide an explanation for the co-crystallization
of large amounts of pyrochlore and fluorapatite in
some of the ring-dykes at Bonga. However, other
possible mechanisms for F removal are by
reaction with the host rock during fenitization or
by exsolution. A higher degree of interaction with
the host rocks can be expected in the ring dykes in
comparison to the central intrusions; exsolution of
F is likely to occur during volcanic processes.
Primary crystallization of Ta-rich pyrochlore or
microlite takes place at higher temperatures than
Nb-rich pyrochlore (Kjarsgaard and Mitchell,
2008); this trend has been recorded in some of
the aforementioned carbonatites but not in the
Angolan cases.
Fluorine has an important role as a complexing
anion for HFSEs and REEs in alkaline and acidic
environments (Montero et al., 1998; Agangi et al.,
2010). The enrichment of HFSEs and REEs in the
rims of the volcanic pyrochlore from Catanda
might be better explained by the exsolution of a
F-rich fluid phase from the carbonatite magma
 A. C. J. M. BAMBI ET AL.

FIG. 5. Bivariate plots of F vs. occupancy in the A site, expressed in a.p.f.u.: (a) F vs. Na; (b) F vs. Ce; (c) F vs. Th;
(d) F vs. U; (e) F vs. vacancies at the A site; and (f) F vs. Ca.

388
 F IN CARBONATITIC PYROCHLORE

and the formation of F-complexes. These
elements would partition into the residual fluids.
Textural evidence shows that this process and the
crystallization of the rims took place before the
carbonatite magma erupted as brecciation post-
dates the development of the rims.
Conclusions
The compositions of pyrochlore in the intrusive
rocks from Tchivira and Bonga are comparable,
whereas major differences are present in the
pyrochlores from the extrusive carbonatites at
Catanda. Two types of trend can be identified
from the intrusive to the extrusive carbonatites:
(1) enrichment in HFSE and REE; and (2) impov-
erishment in F and Na.
These trends can be explained by changes in
the F activity in the magmas. In the plutonic
Tchivira carbonatites fluornatropyrochlore, which
contains very small amounts of HFSEs and REEs,
is present. The hypabyssal Bonga carbonatites
contain fluorcalciopyrochlore with less F than
Tchivira, in accordance with a higher degree of
fenitization and extensive fluorine-rich apatite
precipitation. These pyrochlores are slightly

FIG. 6. Bivariate plots of F versus occupancy in the B site, both expressed in a.p.f.u.: (a) F vs. Nb; (b) F vs. Ta;
(c) F vs. Zr; (d) F vs. Ti.

389
 A. C. J. M. BAMBI ET AL.
enriched in HFSEs and REEs relative to Tchivira.
The most striking compositional changes
observed are in the volcanic carbonatites from
Catanda. The pyrochlore cores are fluorcalciopyr-
ochlore and they have HFSE and REE contents
that are similar to the pyrochlore crystals from
Bonga, suggesting the early formation of pyro-
chlore as a liquidus mineral in a deep magmatic
chamber. However, the hydroxycalciopyrochlore
rims are strongly depleted in F and enriched in
HFSEs and REEs, suggesting that this generation
of pyrochlore crystallized following the extensive
removal of F by exsolution. This exsolved fluid
complexed the HFSEs and REEs and together
with changes in the F activity this resulted in the
crystallization of a late generation of pyrochlore
enriched in these incompatible elements.
Acknowledgements
This research was supported by the projects
CGL2006-12973 and CGL2009-13758 of the
Ministerio de Educación y Ciencia of Spain and
SGR 589 and SGR 444 of the Generalitat de
Catalunya. Logistical assistance for the field trips
was provided by the Departmento de Geologia da
Universidade Agostinho Neto (Luanda, Angola).
The studies of A. Bambi in Barcelona were
supported by an AECI grant; A. Costanzo
acknowledges financial support provided by the
SYNTHESIS (Project GB-TAF-3835) and in
particular Dr C.T. Williams for the assistance
received at the Natural History Museum in
London. Dr Xavier Llovet assisted in the EPMA
analyses at the Serveis Cientı́fico-Tècnics,
Universitat de Barcelona.
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