28 Magmatic ore deposits

elements of atomic number Z ¼ 57 (La) to Z ¼ 71 (Lu), the LREEs are the lower-
atomic-number elements in this row (La, Ce, Pr, Nd, Sm and Eu) and the heavy
rare-earth elements (HREEs) are those from Gd to Lu. Because they have the same
outer-shell electron configuration, the REEs exhibit very similar chemical behaviour in
natural environments and readily substitute for each other in minerals. All form ions
with þ3 charge, although two, Eu and Ce, can also be present in natural environments
with þ2 and þ4 charge, respectively. The increasing atomic number is taken up by
addition of electrons to the inner 4f electron shell; this causes progressive reduction in
ion size across the row, and hence differences in partitioning constants which allow
partitioning of the LREEs from the HREEs. The HREEs are less abundant than LREEs
in the crust, and are most strongly concentrated in different types of ores than the
LREEs (see page 337 in Chapter 6).

The nature of typical carbonatites and hosted LREE ores

Intrusive carbonatites occur most typically as roughly cylindrical, composite, approxi-
mately pipe-shaped, steeply plunging stocks up to about 3 km in diameter, although they
can also occur as irregular lenticular bodies (Figure 2.3). Swarms of carbonatite dykes are
often present within a few kilometres of larger intrusions. Some carbonatites are isolated
intrusions, but most are adjacent to or within complex zoned intrusions of mafic and
ultramafic alkaline intrusive rocks. The rocks located within a few hundred metres of the
contacts of carbonatite intrusions and of zoned intrusions of carbonatite and alkaline
silicate igneous rocks are in almost all cases converted to fenite. This is a metasomatic
rock type characterised by high potassium content, such that one or more of K-feldspar,
riebeckite, and biotite are important minerals.

W E

Mesoproterozoic Mountain Pass Carbonatite

Bastnaesite calcite carbonatite
Bastnaesite dolomite calcite carbonatite
Bastnaesite dolomite carbonatite
Monazite carbonatite
Breccia - fenite altered gneiss clasts in
50 m carbonatite matrix
Palaeoproterozoic
Gneiss

Figure 2.3 Cross section through the open pit of the Mesoproterozoic Sulfide Queen
carbonatite intrusion at Mountain Pass, California, USA (after Castor, 2008) showing
characteristic heterogeneity of these intrusions. The ore zones are essentially the three
bastnaesite-bearing units within the intrusion.

Downloaded from Cambridge Books Online by IP 158.109.192.111 on Thu Jan 09 15:25:51 WET 2014.
http://dx.doi.org/10.1017/CBO9781139135528.003
Cambridge Books Online © Cambridge University Press, 2014
29 2.2 Types of magmatic ore deposits

On average, carbonatites have the highest concentrations of rare-earth element oxides

(REOs) of all crustal rock types. Summed REO concentration is about 0.5%, which is
around 30 times that of average continental crust. In unweathered REE-rich igneous
carbonatite, the REEs are hosted in different minerals in which they are essential
components, especially the REE fluorocarbonates bastnaesite [(La,Ce)CO3(F,OH)] or
more rarely parisite [Ca(Ce,La)2(CO3)2F2], or the phosphate monazite [(Ce,La,Th)PO4].
The ores have igneous textures with the ore minerals either disseminated relatively
uniformly or as concentrations in clusters with other minerals through the carbonatite.
Economic ores of LREEs are hosted in the small number of carbonatites that have
significantly higher concentrations in part or all of the intrusion, with grades of up to a few
weight per cent (wt %) combined LREEs. At Mt Weld, ore is in weathered carbonatite
and the enrichment to ore grade is a result of lateritic weathering (see Section 6.1). In
contrast, the high concentrations of LREEs at Bayan Obo and Mountain Pass occur in
rocks with essentially fresh igneous minerals and textures and the ores are thus interpreted
as ‘primary’ magmatic ores. These two LREE ore-bearing carbonatites are unusual
compared to other carbonatites. At Mountain Pass (Figure 2.3), ore is in calcitic and
dolomitic carbonatite with barite as an important gangue mineral. The carbonatite is
unusually associated with an ultrapotassic alkaline intrusion. At Bayan Obo, ore is present
in calcite carbonatite, but the highest grades are in composite lenses of unique iron oxide–
fluorite–aegerine-augite rock which is hosted within a large (10 by 2 km outcrop area)
carbonatite intrusion. Other carbonatites with high primary REE concentrations are
known but many have not been fully evaluated as possible deposits of REEs, for instance,
along the East African Rift and at Kanneshin (Afghanistan).

Genesis of LREE ores in carbonatites

The environments of melting to form carbonatite magmas are inferred using geochem-
ical reasoning and through comparison of rock compositions with results of petrological
experiments of melting at high pressures. At pressures greater than about 2.5 GPa,
hence depths greater than about 90 km, dolomite can be a stable mineral in mantle
peridotite. Up to a few per cent of carbonate is present in some mantle-derived
xenoliths, hence suggesting that it is a minor component of some mantle peridotite.
Carbonatite melts are produced in experiments by low percentages of partial melting of
carbonate-bearing peridotite at between about 2.5 GPa and 6 GPa. The carbonate
minerals are fully melted after a few per cent partial melting, and the maximum
percentage of melting that will produce a carbonatite melt from dolomite-bearing
mantle peridotite is thus estimated to be less than about 3%. With slightly higher
temperatures and degrees of melting, the same source rock will produce carbonate-
bearing alkaline magmas (Figure 2.4). As the solidus is at a higher temperature at lower
pressures (Figure 2.4) carbonatite melts may in most cases freeze on rising through the
upper mantle and may only reach the surface in unusual circumstances of rapid rise
from the depths of melting.
The geochemical behaviour and mineralogical setting of REEs in mantle environments
is not fully known; however, their likely behaviour on melting can be interpreted. All
REEs have ionic radii too large for easy substitution in crystal lattice sites in major mantle
minerals, and unless there is a minor mineral in which they are compatible they will be
incompatible and will be concentrated in a melt. Partition coefficients are lower for

Downloaded from Cambridge Books Online by IP 158.109.192.111 on Thu Jan 09 15:25:51 WET 2014.
http://dx.doi.org/10.1017/CBO9781139135528.003
Cambridge Books Online © Cambridge University Press, 2014
30 Magmatic ore deposits

Ci,melt
~80
8.0 Ci,0

elts
20
Cmelt

s
1

cm
elt
solid mantle =

cm
C0 [D+F(1–D)]

alti
titi
6.0

bas
Magnesite lherzolite

na
rbo

ali
(Ol+Opx+Cpx+Grt+Mgs)

alk
ca
Pressure, GPa

La, D=0.002

Ci,melt
Ci,0
4.0 px
s+C Grt
Mg x+Ol+ 10

10%

20%

40%
1%
5%
p
+O
Dol Eu, D=0.04
Dolomite lherzolite

1%
Opx
2.0 Dol+ rt+CO 2 percentage melting

5%
O l+ G compatible
+
Cpx

15%
elements
Lherzolite + CO2 partially molten
(Ol+Opx+Cpx+Grt+CO2) mantle Lu, D=0.8
D=5
0
0 0 1
1000 1200 1400 1600 F: fraction melted
(batch melting)
Temperature °C

Figure 2.4 Left: Schematic pressure–temperature diagram of the environment of formation

of carbonatitic and alkali–basaltic melts from carbonate-bearing mantle peridotite (dolomite
and magnesite lherzolite), after Dalton and Presnall (1998). Numerical percentages of partial
melts at any pressure and temperature, and the boundary between carbonatitic and basaltic
melts are based on experiments with 2.5 wt % CO2 of Dasgupta et al. (2007). The exact
positions of these isotherms will depend on the modal per cent carbonate in the mantle and are
shown to illustrate trends only. Right: Element enrichment in melt compared to source rock
as functions of fraction melted (F) and bulk partition coefficient (Di) for the rare-earth
elements La, Eu and Lu, based on the equation for batch (one-step) partial melting, as shown.
The shaded circles correspond to melt extraction at the conditions shown on the P–T diagram.
Partition coefficients are taken from Dasgupta et al. (2009).

LREEs than for HREEs, hence the former will be more strongly concentrated in melts.
The concentrations of LREEs in typical carbonatites and the relative concentration of
LREEs over HREEs are of the order that is expected in low-percentage batch partial melts
of carbonate-bearing mantle peridotite (Figure 2.5).
Small degrees of partial melting of mantle with average REE concentrations can
produce melts with approximately 0.5% REOs. Additional processes are, however,
required to produce enrichment from about 0.5% to per cent levels of LREEs in ores.
Most carbonatites in the upper crust are not primitive magmas whose composition is
unchanged between formation of melt in the mantle and final crystallisation in the upper
crust, but have evolved through fractional crystallisation and other petrogenetic processes,
probably at various depths in the upper mantle and in the crust. Processes that could cause
enrichment to per cent levels of LREEs include fractionation during crystallisation,
immiscible separation of alkaline silicate melts and carbonatite melts, and hydrothermal
processes. At both Bayan Obo and Mountain Pass there are multiple phases of carbonatite
dykes; later dykes have higher concentrations of REEs, a fact that suggests fractional
crystallisation was a contributing process in the formation of these ores (see discussion of
this process in Section 2.2.5).

Downloaded from Cambridge Books Online by IP 158.109.192.111 on Thu Jan 09 15:25:51 WET 2014.
http://dx.doi.org/10.1017/CBO9781139135528.003
Cambridge Books Online © Cambridge University Press, 2014