Evolution of Carbonatite

Magmas in the Upper Mantle

and Crust
Gregory M. Yaxley1, Bruce A. Kjarsgaard2,3, and A. Lynton Jaques1

1811-5209/21/0017-0315$2.50  DOI: 10.2138/gselements.17.5.315

C
arbonatites are the most silica-poor magmas known and are amongst and their intrusive equivalents).
The most common are nephe-
Earth’s most enigmatic igneous rocks. They crystallise to rocks dominated
linite, syenite, and melilitite, the
by the carbonate minerals calcite and dolomite. We review models for parental melts of which could have
carbonatite petrogenesis, including direct partial melting of mantle litholo- been derived by small degrees of
partial melting of the hydrous-
gies, exsolution from silica-undersaturated alkali silicate melts, or direct
and carbonate-bearing mantle
fractionation of carbonated silicate melts to carbonate-rich residual melts. (Woolley and Kjarsgaard 2008).
We also briefly discuss carbonatite–mantle wall-rock reactions and other Progress towards understanding
the formation and evolution of
processes at mid- to upper crustal depths, including fenitisation, overprinting
carbonatite magmas has been
by carbohydrothermal fluids, and reaction between carbonatite melt and complicated by their petrological
crustal lithologies. diversity and that of the associ-
ated silicate rocks, and by the
Keywords: carbonatite; partial mantle melts; liquid immiscibility; fractionation;
common presence of cumulate,
SiO2-undersaturated melts.
flow banded, and rheomorphic
textures in carbonatites. Field,
INTRODUCTION petrological, and geochemical studies have shown strong
Carbonatites are silica-poor igneous rocks composed links between carbonatites and their associated alkaline
predominantly of primary carbonate minerals, typically silicate rocks. These carbonatite–alkali–silicate complexes
>50% modal calcite and dolomite. They are the most silica- could be related by liquid immiscibility, or by extensive
undersaturated magmas in the Earth’s crust. The bulk of fractionation of CO2 -bearing silicate melts that have left
the worlds’ supply of rare earth elements (REEs) and Nb is residual carbonate-rich liquids. Alternatively, some carbon-
derived from carbonatites. The Earth has approximately atites occur without associated silicate rocks and/or carry
600 known occurrences of carbonatites (Humphreys- mantle xenoliths and xenocrysts and are inferred to be
Williams and Zahirovic 2021 this issue) that range in derived directly from the mantle (Harmer and Gittins
age from Archean to the present day, and are found on 1997). These carbonatites crystallise magnesian calcite as
all continents and, in rare cases, on oceanic islands with the liquidus phase at low pressures (Harmer and Gittins
atypically thick lithosphere [i.e., the Canary Islands (Spain) 1997) and this, coupled with field and textural evidence for
and Cape Verde]. The most common geodynamic setting cumulates and crystal mushes, lends support for a primary
for carbonatites is within intraplate regions, commonly mantle origin for some carbonatites. Furthermore, these
cratonic margins, and many are associated with the early primary carbonatites may sometimes be spatially ‘associ-
stages of rifting and plate separation. Carbonatites have ated’ with primary alkali silicate rocks, but have no genetic
been linked to mantle plumes and the formation of large relationship to them.
igneous provinces (Bell and Simonetti 2010). Despite their diversity in mineralogy and lithological
Carbonatites are a diverse group of rocks that include extru- association, most carbonatites have stable (carbon and
sive, intrusive, and carbohydrothermal varieties (formed oxygen) and radiogenic isotopic compositions that
by reaction with CO2 + H 2O–rich fluids). The only known unequivocally indicate a mantle origin for their parental
currently active carbonatite volcano is Oldoinyo Lengai magmas (e.g., Bell and Simonetti 2010). Moreover, young
(Tanzania), which historically erupted natrocarbonatite. (<200 Ma) carbonatites have Sr, Nd, and Pb isotopes that
However, there are ~50 examples of carbonatite extrusives closely resemble those of oceanic islands basalts, with
reaching back to 1.8 Ga in the geological record. HIMU (‘high μ’, where μ = 238U/204Pb) and EM1 (‘enriched
The majority of carbonatites (74%) are associated with a mantle type 1’) being the dominant mantle endmembers.
wide variety of alkaline igneous silicate rocks that range This suggests they contain significant components that
from ultramafic to felsic (e.g., lamprophyres, olivine originated in the sub-lithospheric mantle. Noble gas and
­melilitites, olivine nephelinites, phonolites, syenites, N isotopic compositions also indicate a sub-lithospheric
source for the parental melts, associated with either
upwelling asthenospheric mantle or with plumes arising
1 Australian National University from the deeper mantle (Bell and Simonetti 2010).
Research School of Earth Sciences
Acton ACT 2601, Australia The aim of this article is to review models for the petro-
E-mail: greg.yaxley@anu.edu.au genesis of carbonatites and their evolution before and
2 Geological Survey of Canada during crustal intrusion or eruption. Current models for
601 Booth Street the genesis of carbonatites are illustrated in Figure 1 and
Ottawa, Ontario, Canada include the following:
3 University of Alberta
Department of Earth and Atmospheric Sciences 1. Primary carbonatite magmas emplaced into the crust
Edmonton, Alberta, Canada directly from their mantle sources. Partial melting of

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 carbonate-bearing peridotite or eclogite in the mantle
has been shown to produce alkali-bearing, dolomitic
to calcio-dolomitic melts (e.g., Wallace and Green 1988;
Yaxley and Brey 2004).
2. Separation of an immiscible carbonatite magma from
CO2 -bearing, silica-undersaturated, silicate magmas
(e.g., Freestone and Hamilton 1980). Immiscibility is
induced by fractionation of the parental primary or
evolved liquid, driving its composition to a two-liquid
solvus leading to separation of silica-undersaturated
silicate melt and carbonatite melt (Kjarsgaard and
Peterson 1991; Brooker and Kjarsgaard 2011).
3. Residual melts from the fractional crystallization of
evolved, carbonated, undersaturated, alkali-rich silicate
liquids without immiscibility (Watkinson and Wyllie
1971).
In any of these three cases, the parental carbonatite and
alkali silicate melts may be further modified in the upper
mantle or crust by fractional crystallization, reaction
with and/or assimilation of wall rock, and loss of alkali-
rich fluids to surrounding crust via a process referred
to as fenitisation. Extended fractionation of sodic or
potassic alkaline silicate magmas (and of carbonatites
themselves) can produce low-temperature CO2, H 2O-rich
(and F-rich) residual fluids, commonly referred to as carbo-
hydrothermal fluids (Woolley and Kjarsgaard 2008). These
fluids may precipitate carbonates, and also can, thus, form
‘carbonatite rocks’. Whether these are residual melts (also
called ‘brine-melts’) or residual fluids is a topic of ongoing
research and debate (e.g., Anenburg et al. 2020a).
We will review evidence from experimental petrology,
geology, and geochemistry for these models (Fig. 1) and
demonstrate that they all apply in different situations.
CARBONATE MELTS FROM THE MANTLE
Evidence from high-pressure experimental petrology
has shown unequivocally that in both compositionally
simple systems such as Na 2O–CaO–MgO–SiO2–CO2 and
in “complex” natural systems with ≥10 major and minor
components, low degrees of melting of carbonate-bearing
peridotite or eclogite can produce alkali-bearing, dolomitic,
and calcio-dolomitic carbonate melts. The melts form at
a pressure (P) ≥2 GPa (Fig. 2) and a temperature (T) and
oxygen fugacity that occurs along oceanic and continental
upper mantle conductive geotherms (Wallace and Green
1988; Dasgupta et al. 2004).
A B
Carbonatite melt Fenitized crust
Continental crust conduits
Continental crust
Continental
lithospheric mantle Carbonated
silicate melt
Apatite-bearing
Metasomatised wehrlite
Continental
peridotite Amphibole peridotite +
carbonatite melt
lithospheric mantle
Hot adiabatically upwelling mantle Metasomatized
conduit
Schematic diagrams illustrating three models for
Figure 1
carbonatite formation. (A) Partial melting of amphi-
bole carbonate peridotite induced by heat influx from upwelling
asthenospheric mantle forms ephemeral sodic dolomitic carbon-
atite melt, which ascends and reacts with lithospheric orthopy-
roxene, forming a wehrlite layer. If wehrlite armours the magma
conduits then dolomitic carbonatite may reach the crust. Reaction
of dolomitic carbonatite and wehrlite can generate calciocarbonites
that may also reach the crust. Alternatively, rapid ascent through
lithosphere-scale fractures (thick black lines) may allow direct
crustal emplacement. (B) Fractional crystallisation involving olivine
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Melting of carbonate peridotite near its solidus to produce
carbonate melts is limited to pressures ≥2.0 GPa, where the
reaction
4MgSiO3(opx) + CaMg(CO3)2(melt) =
2Mg2 SiO4(ol) + CaMgSi2O6(cpx) + 2CO2(fluid) (1)
intersects the peridotite + CO2 ± H 2O solidus and limits
dolomite stability relative to CO2 -rich fluid at lower
pressures (Fig. 2). At higher pressures and subsolidus
temperatures, magnesite forms via the vapour-absent
reaction
CaMg(CO3)2(dolomite) + 2MgSiO3(opx) =
CaMgSi2O6(cpx) + 2MgCO3(magnesite) (2)
Near-solidus melts from 2 to 6 GPa are dolomitic to calcio-
dolomitic, with SiO2 ~5%‒10%, Ca/Mg <1, and a total alkali
content of typically 5‒7 wt% (Wallace and Green 1988;
Dasgupta et al. 2004) (Fig. 2).
Carbonatite melts are of very low density and viscosity and
are able to wet silicate grain boundaries at melt fractions as
low as 0.02% (Hunter and McKenzie 1989). They can, there-
fore, segregate from their sources at near-solidus condi-
tions and, being buoyant, can migrate rapidly along silicate
grain boundaries by porous flow. If dolomitic carbonatites
ascend at such low melt fractions, they are likely to migrate
along P–T paths close to the local geotherm, rather than
along liquid adiabats. When they intersect Reaction (1),
the dolomite component in the carbonatite melt will
react with, and replace, orthopyroxene in the wall rock to
produce metasomatic olivine and clinopyroxene, releasing
a CO2-rich fluid. This process may even eliminate orthopy-
roxene locally, leading to the formation of apatite-bearing
wehrlite, as has been documented in spinel-peridotite
xenolith suites from eastern Africa and southeastern
Australia (Yaxley et al. 1991; Rudnick et al. 1993).
Clearly, in this situation, Reaction (1) represents a barrier to
migration through, and the extraction of, carbonatites and
carbonated undersaturated silicate melts from lherzolitic
or harzburgitic mantle. However, Dalton and Wood (1993)
showed that the conversion of peridotite to wehrlite, which
can result from Reaction (1), may armor magma conduits
and pathways and thereby allow their ascent, without
intersecting Reaction (1). Instead, dolomitic carbonatite
melts can evolve to more CaCO3 -rich compositions by
reacting with the wehrlite wall rock (Dalton and Wood
1993) (Reaction 3).
Carbonatite Carbonatite liquid
C Calcite
liquid
Clinopyroxene Continental Continental
crust crust
Nepheline
Olivine
Magma conduit/
chamber
(quadrilaterals, no cleavage), clinopyroxene (hexagons, oblique
cleavage), and nepheline (elongate octagons, orthogonal
cleavage) in a silica-undersaturated, carbonated silicate melt drives
the liquid to a two-liquid solvus, allowing carbonatite liquid to
unmix and segregate. The outer patterned margin of the carbon-
atite represents fenite (and fenitization) in the crust and metasoma-
tism of a magma conduit in the mantle. (C) Fractional
crystallisation of a silica-undersaturated, carbonated silicate melt
leads to highly evolved, carbonatite liquid without intersecting a
solvus. The indicated crystals are as for Figure 1B but with the
addition of calcite (rhombs with oblique cleavage).
316 O c tober 2021

Peridotite–COH melting relations. Low-temperature
Figure 2
field is subsolidus peridotite. The black line is the
oxidised (carbonate stable) solidus of peridotite + CO2 + H2O. The
stippled field corresponds to residual amphibole peridotite in
equilibrium with carbonatite melt and is bounded to higher T and P
by the amphibole dehydration curve (dashed curve). Also shown
are the oxidized solidus of peridotite + CO2 + H2O fluid at lower
pressures and the reduced solidus of peridotite + CH4 ± H2O at
higher pressures. The solid, steep straight line is a mantle adiabat
with potential temperature (Tp) of 1,350 °C; a representative
geotherm for cratonic lithospheric mantle is also shown. The lines
in the sub-solidus field represent Reactions (1) and (2).
Abbreviations: opx = orthopyroxene; cpx = clinopyroxene.
After Foley et al. (2009).
3CaMg(CO3)2(melt) + CaMgSi2O6(cpx) =
2Mg2 SiO4(ol) + 4CaCO3(melt) + 2CO2(fluid) (3)
The spatial relationship of carbonatites to crustal-scale
faults or structures, coupled with buoyant magma rapidly
transported through the mantle lithosphere, may also
hinder Reactions (1) and (2), allowing alkali-bearing
dolomitic magmas to reach high crustal levels or the
surface (Fig. 1).
The HIMU isotopic signature of oceanic islands basalts
suggests that they are derived from mantle sources
containing ancient recycled oceanic crust. An alterna-
tive model for the formation of carbonatites is by partial
melting of carbonate-bearing eclogite in the upper mantle
(Dasgupta et al. 2004; Yaxley and Brey 2004). In this
model, carbonated eclogite derived from subducted altered
oceanic crust is recycled back into the mantle and stored
for billions of years in the mantle before being incorpo-
rated into carbonatite source regions. Experiments have
shown that carbonatite melts can be formed by partial
melting of carbonated mantle eclogite (Dasgupta et al.
2004; Yaxley and Brey 2004). These studies have shown that
near-solidus melts at 2.5 GPa to 5.0 GPa are sodic calcio-
dolomitic carbonatites, and are markedly more calcic
than the dolomitic melts produced by partial melting of
carbonated peridotite. Yaxley and Brey (2004) suggested
that carbonatite liquids formed from carbonated eclogite
heterogeneities in ambient peridotite mantle may freeze to
dolomite or magnesite when segregating from the eclogite
source and percolating into any surrounding peridotite
wallrock. Alternatively, the carbonatites may remain liquid
and then migrate to the surface.
CARBONATE MELTS FORMED VIA LIQUID
IMMISCIBILITY
Carbonatite liquids can form from carbonated silicate
magmas if such magmas reach the two-liquid solvus that
separates carbonate and silicate liquids. Melting of perido-
tite with only a few 1,000 ppm C, at low melt fractions
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and high pressures (≈2.5–3.5 GPa) yields carbonated,
SiO2 -undersaturated silicate melts, such as olivine melil-
itite or olivine nephelinite (Green 2015), with several wt%
dissolved CO2 . Segregation and migration of these melts
into the crust, coupled with crystal fractionation of silicate
phases, increases CO2 in the residual silicate liquid such that
a carbonate liquid is exsolved. Thus, a carbonatite magma
forms, with its associated conjugate silica-undersaturated
silicate magma (e.g., Kjarsgaard et al. 1995; Weidendorfer
et al. 2016).
There have been numerous experimental studies on the
immiscibility of silicate–carbonate liquids at crustal and
upper mantle pressures (see Brooker and Kjarsgaard 2011
and references therein). These studies have been broadly
aimed at understanding the effects of variable bulk compo-
sitional parameters [alkali, SiO2 and H 2O contents, Ca/Mg,
Fe/Mg, pressure (including PCO ) and temperature] on the
2
extent of the carbonate–silicate two-liquid field, and the
compositions of liquids and solid phases.
Experimental studies at crustal pressures using natural rock
powders have shown that immiscibility between silicate
and carbonatite melts can reproduce compositions closely
resembling those found in nature (Freestone and Hamilton
1980; Kjarsgaard and Peterson 1991). The rock composi-
tions used as starting material in the two-liquid experi-
mental studies include nephelinite or phonolite combined
with natrocarbonatite from Oldoinyo Lengai (Freestone
and Hamilton 1980; Kjarsgaard et al. 1995) and nephelin-
ites from the Shombole Volcano (Kjarsgaard and Peterson
1991). These studies indicate that the immiscibility field
closes off at low alkali contents with the production of
conjugate Na-bearing calcic carbonatites and nephelin-
ites. They also indicated that the two-liquid field narrows
in compositional space with increasing temperature and
decreasing pressure (Fig. 3). Notably, liquid immiscibility,
while feasible at mantle pressures (2‒3 GPa), is favoured at
moderate pressures (mid-crust to lower-crust). At mantle
pressures, high CO2 solubility in the silicate melt may
preclude CO2 -saturation and immiscibility (Brooker and
Kjarsgaard 2011).
Strong support for the important role of liquid immisci-
bility in the generation of carbonatites associated with
alkaline silicate magmas is provided by an analysis of ocean
island volcanics by Schmidt and Weidendorfer (2018), who
showed that the formation of carbonatites is restricted to
those hotspot islands which have lavas with the lowest Si-
and highest alkali-contents among their primitive melts
(Cape Verde and Canary Islands). In these cases, crystal
fractionation of strongly silica-undersaturated primitive
melts having high alkali contents drives the evolving melts
into the silicate–carbonatite miscibility gap, whereas less
alkaline magmas fractionate toward the alkali-feldspar
thermal divide and do not exsolve a carbonatite.
The carbonatite lavas erupted from Oldoinyo Lengai are
also considered to result from liquid immiscibility with
the carbonatite exsolved from parental nephelinite magma
(Potter et al. 2017). Supporting evidence is found in melt
inclusions trapped in minerals crystallising from the lavas
(e.g., gregoryite, schorlomite, nepheline, clinopyroxene)
which preserve clear textural evidence of immiscibility
between nephelinitic and carbonatite (and halide) liquids
(Potter et al. 2017). The lavas erupted at Oldoinyo Lengai
contain phenocrysts of gregoryite [(Na 2K 2 Ca)CO3] and
nyerereite [Na 2 Ca(CO3)2] in a complex groundmass of
Na–Ca-carbonate solid solutions, Na 2CO3, khanneshite,
fluorite, Na-sylvite, K-halite, apatite, nepheline, sulfides,
and other phases (Potter et al. 2017; Weidendorfer et al.
2017; Kamenetsky et al. 2021 this issue). The origin of the
carbonatite lavas ultimately relates to liquid immiscibility
from parental nephelinite magma that exsolved alkali-
carbonate liquid.
317 O c tober 2021
 The highly sodic carbonatite lavas at Oldoinyo Lengai
are commonly viewed as anomalous because they do
not resemble any other carbonatites, which are typically
much lower in Na 2CO3 and richer in CaCO3. The majority
of carbonatites are alkali-depleted due to many possible
processes, e.g., accumulation of crystallized calcite or
dolomite, alkali loss to exsolved fluids or late-stage melts, or
even weathering. The lavas of Oldoinyo Lengai are notori-
ously unstable under atmospheric conditions and are diffi-
cult to preserve in the surficial environment because of the
H 2O-soluble nature of the sodic carbonate minerals they
crystallise. The lavas have been observed to evolve very
rapidly after eruption as a result of alkali leaching, leaving
residual calcic carbonate rocks, with the primary melt
compositions only preserved as inclusions in minerals.
An example of carbonatite formation by silicate–carbonate
liquid immiscibility as recorded in melt inclusions is the
Kerimasi Volcano (Tanzania), only a few kilometres south
of Oldoinyo Lengai. At Kerimasi, melt inclusions trapped
in perovskite consist of immiscible silicate–carbonate
pairs: melilitite and conjugate alkali-bearing (7‒10 wt%)
calciocarbonatites (Guzmics et al. 2015). However, silicate
and carbonate melt inclusions in nepheline, apatite, and
magnetite further reveal a range of compositions, including
melt inclusions similar to the natrocarbonatites that
erupted from Oldoinyo Lengai (Guzmics et al. 2015). The
difference in exsolved carbonatite compositions is attrib-
uted to the more calcic parental melilitite at Kerimasi
Volcano compared with the peralkaline nephelinite parent
at Oldoinyo Lengai. This illustrates the important effects
of the parental undersaturated alkali silicate melt compo-
sition on the nature of the exsolved conjugate carbonate
liquids (Kjarsgaard and Peterson 1991).
Na2O Na2CO3
+ K2O
C CL: Lengai 2-liquid experiments
ca
rbo
CL
na
D
te
Cpx SL
lim
b
SL
Cc CL CL
CL
50
Oldoinyo Lengai
2-liquid field
0.3 GPa, 1,100o C
1,250
0
900 silic
ate
limb
A 900
Shombole 2-liquid field, 0.5 GPa
polythermal 1,025-900 oC
1,025
2–3 G
Pa 2-l
iquid
field
SiO2+ TiO2+ Al2O3 50
(A) Silicate–carbonate two-liquid fields, as deter-
Figure 3
mined from experiments, plotted on the Hamilton
ternary, projected from CO2 (± H2O). The Oldoinyo Lengai
(Tanzania) two-liquid field for moderate- to high-alkali composi-
tions at fixed P (0.3 GPa) and T (1,100 °C) is shown by filled stars
connected by conjugation (tie) lines. Decreasing temperature from
1,250 °C to 900 °C (open stars) at fixed P and X illustrates the
widening of the two-liquid field. Data from Freestone and
Hamilton (1980). The low-alkali Shombole (Kenya) two-liquid
solvus at 0.5 GPa (polythermal, 1,025‒900 °C), and a 2‒3 GPa,
1,250 °C mantle pressure solvus illustrates the increased size of the
two-liquid field with increasing pressure from 0.3 to 3 GPa. Data
from Kjarsgaard (1998) and Brooker and Kjarsgaard (2011).
(B) Carbonate liquid (CL) compositions plotted on the K-poor part
of the CaCO3 –Na2CO3 –K 2CO3 ternary at 0.1 GPa. The calciocarbon-
atite to natrocarbonatite differentiation trend (illustrated by a red
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FRACTIONAL CRYSTALLISATION OF
SILICATE MELTS LEADING TO RESIDUAL
CARBONATITE MELTS
In some cases, silica-undersaturated alkali melts may
undergo fractional crystallisation without intersecting a
two-liquid field. Fractionation may proceed sufficiently
to produce an evolved, residual carbonatitic liquid.
Experimental studies of this process are rare. Watkinson
and Wyllie (1971) investigated the nepheline–calcite join
at 25 wt% H 2O and showed that a H 2O-bearing liquid with
a composition of 90% nepheline + 10% calcite at ~0.1 GPa
could undergo fractionation with a successive assemblage
of nepheline, melilite, and hydroxyhaüyne or cancrinite,
leading to a calcite-rich residual liquid. This was a way to
explain the sequence of rock-types observed in the Oka
carbonatite complex in Quebéc (Canada), where nephe-
line-, melilite + nepheline-, melilite + hydroxyhaüyne or
cancrinite-, and calcite + cancrinite + melilite-bearing
rocks correspond, respectively, to the ijolite, nepheline–
okaite, okaite, and carbonatite. Further experimental
work is necessary to assess the characteristics of CO2 - and
H2O-bearing silicate melt compositions, their fractionating
phases, and the pressure–temperature conditions that
might allow for liquid lines of descent that do not intersect
a two-liquid solvus, thereby evolving all the way to residual
carbonatite liquids without immiscibility.
CARBONATITE MAGMA DIFFERENTIATION
The fact that many carbonatites in the Earth’s crust are rich
in CaCO3 (sövites, or calciocarbonatites) is consistent with
their derivation as calcite cumulates from broadly dolomitic
parental melts (Harmer and Gittins 1997). As described
earlier, melts parental to carbonatites that formed in the
K2CO3
CL: Shombole 2-liquid experiments
CL: Kerimasi melt inclusion
CL: Calcite-saturated experiments
Sodium carbonate–Gregoryite ss + liquid
Nyerereite–Fairchilditess + liquid
Oldoinyo
Lengai Calcioarbonatite melt
lavas differentiation trend
Na 2
THERMAL DIVIDE
Ca
ite tectic
(C
Nyerere co
3
O3 2
Calcite
KC
)
850
890
900 1,000
Calcite + liquid
B
1,025
1,320 oC
CaO + FeO + MgO CaCO3
dashed line + arrow) is due to suppression of the calcite–nyerereite
cotectic and nyerereite–fairchildite thermal divide in a natural
system. Modified after Kjarsgaard and Peterson (1991) and
Weidendorfer et al. (2017). Calcite-saturated carbonate liquid
experimental data after Weidendorfer et al. (2017); carbonate
liquids from Kerimasi melt inclusions from Guzmics et al.
(2015); carbonate liquids from two-liquid pairs from Freestone
and Hamilton (1980) and Kjarsgaard (1998). (C) Reflected light
image of an experimental run product showing quenched immis-
cible silicate liquid (SL) and carbonate liquid (CL) from an experi-
ment run at 1.5 GPa, 1,275 °C in the system SiO2–Na2O–Al2O3 –CO2.
Courtesy of Richard Brooker. (D) Image of experimental run
with immiscible silicate liquid (SL) and carbonate liquid (CL) and
crystals of clinopyroxene (Cpx) and calcite (cross polarized light).
From Shombole nephelinite run BK290; B.A Kjarsgaard,
unpublished.
318 O c tober 2021
 mantle are likely to be alkali-dolomitic to calcio-dolomitic
in composition. Liquids close to the compositional join
CaCO3–MgCO3 are unlikely to crystallize dolomite as a
liquidus or sub-liquidus phase at low pressures.
Experimental studies of the alkali carbonate–CaCO3
systems (Weidendorfer et al. 2017 and references therein)
have shown that calcite (and apatite) is a crystallising
phase over a large compositional and temperature range.
Formation of Na-rich carbonatite (similar to those erupted
at Oldoinyo Lengai) from a more calcic parental carbonatite
melt was long considered highly controversial because of
the existence of a thermal barrier in the Na2CO3–K 2CO3–
CaCO3 system at low pressures (see Fig. 3). In this system,
Na-bearing calcic carbonatite liquids would be expected
to crystallise calcite as the liquidus phase and evolve to a
eutectic liquid with <10 mol% Na 2CO3 at about 800 °C, a
substantially lower Na2CO3 content and higher temperature
than the erupted lavas at Oldoinyo Lengai (490‒595 °C).
However, Weidendorfer et al. (2017) have elegantly
demonstrated that when this system includes additional
volatile and other components known to be present in
the natural lavas, such as Cl, F and P2 O5, the thermal
divide is suppressed. They demonstrated that low-pressure
crystallisation of 47.7 wt% calcite, 11.9 wt% apatite and
minor clinopyroxene from a calcitic carbonate liquid with
8‒9 wt% Na 2O + K 2O and as little as 2.7 wt% F and 4 wt%
Cl will terminate at a lower temperature eutectic (≈500 °C)
where a natrocarbonatite melt is saturated in Na 2CO3 and
nyerereite.
This raises the possibility that Oldoinyo Lengai’s highly
sodic lavas are, in fact, not particularly anomalous. The
processes of immiscibility and fractional crystallisation
inferred or observed in this complex may, in fact, be broadly
representative of other Na-poor, calcio-carbonatites which
are associated with silica-undersaturated silicate magmas
and were emplaced in the crust in the geological past. The
low alkali contents of most carbonatites and the rarity of
natrocarbonatites such as those of Oldoinyo Lengai simply
reflects their likely origins as calcite-rich cumulates; a
loss of Na-rich fluids to the surrounding wall rock during
fenitization (see next section); the unstable nature of sodic
compositions and their susceptibility to syn- and postmag-
matic crystallization and fluid alteration, and especially
to weathering and leaching, which may have removed
evidence of their former highly sodic character.
In Figure 4, we illustrate highly simplified versions of
possible scenarios in which carbonatites may be produced,
including by immiscibility from a range of silica-under-
Rift
Continental crust
Lithospheric mantle
Carbonatite
Tholeiites and alkali-basalts Carbonatite
Basanite
Plume head Nephelinite
Melilitite
Metasomatised zone
Asthenosphere
Plume tail
Schematic diagram depicting a section through the
Figure 4
upper mantle (asthenosphere and continental litho-
sphere) with various possible settings for carbonatite formation,
including direct partial melting of carbonated lithosphere near rifts
or cratonic margins (labelled “Carbonatite”) and as a result of
evolution from carbonated silica-undersaturated silicate magmas
(melilitite, nephelinite, basanite). Melting could be induced by a
hot mantle plume impinging on the base of the lithospheric mantle
as shown (or by edge-driven convection). Numbers 1‒4 indicate
the following for the silica-undersaturated magmas:
(1) Approximate relative positions of partial melting; (2) Fractional
crystallisation; (3) Silicate–carbonate liquid immiscibility;
(4) Further fractional crystallisation of the carbonate liquid.
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saturated silicate magmas, and in settings associated with
rifting, mantle plumes, and cratonic margins. In general,
the compositions of the associated silicate rocks are deter-
mined by the thickness of the overlying lithosphere, which
limits the depth and degree of partial melting.
SECONDARY PROCESSES AND CRUSTAL
INTERACTIONS WITH CARBONATITES
Understanding carbonatites and their genesis and evolu-
tion is further complicated by the fact that carbonatites
emplaced at shallow levels in the crust can undergo extensive
re-equilibration and interaction with carbohydrothermal
and other aqueous fluids, including meteoric waters, and
also with the crust into which they are emplaced. A classic
version of these processes is referred to as ‘fenitization’,
whereby an alkali-rich fluid is expelled from the carbon-
atite melt into the surrounding country rock and metaso-
matizes it, forming Na- or K-rich silicate minerals such as
pyroxenes, amphiboles, and alkali feldspars.
Carbonatites commonly display complex multistage
evolutionary histories that can involve magmatic, carbo-
hydrothermal, and hydrothermal stages, which can be
identified by detailed petrological and geochemical study.
Many carbonatites of magmatic origin have been modified
by late-stage magmatic and/or sub-solidus metasomatic
processes involving CO2 -rich and water-rich fluids. These
fluids can lead to the remobilization and formation of
secondary phases and the concentration of REEs, P, Sr,
Ba and F. Experimental studies have shown that REEs are
readily concentrated by hydrothermal processes and that
transport and deposition of REEs is facilitated by forma-
tion of alkali-REE complexes having ligands of Cl−, F − or
CO32− (Anenburg et al. 2020a). In addition to fenitization,
some carbonatites have been inferred to have interacted
so extensively with crustal rocks that they were ephem-
eral, effectively reacting out of existence (Anenburg et al.
2020b).
Hydrothermal processes involving chloride- and carbonate-
rich fluids are thought to have played an important role
in the formation of iron-rich carbonatites (siderite- or
ankerite-bearing carbonatites aka ‘ferrocarbonatites’).
However, iron-rich residual carbonatite could also form
by extended fractional crystallisation of Ca–Mg carbonate
melts, because Fe is highly soluble in residual chloride-
and water-rich carbonate melts. Ferrocarbonatites likely
formed by multistage processes during their crystalliza-
tion, notably involving late overprinting by carbonate- and
chloride-rich hydrothermal fluids and pervasive fenitiza-
tion of the country rock. Similarly, it is clear that multistage
processes involving magmatic carbonatite overprinted by
later carbo-hydrothermal and/or hydrothermal events
4 Craton
commonly play an important role in the development of
3
REE and other associated mineral deposits.
2 CONCLUSIONS AND FUTURE DIRECTIONS
Carbonatites can have multiple origins and complex evolu-
1
tionary histories. Most carbonatites are directly associated
with sodic alkaline silicate rocks (nephelinites, melilitites)
and the case for their formation by liquid immiscibility
Proto-kimberlite is well supported. Much of the compositional diversity of
the more primitive sodic alkaline rock types associated
with carbonatites that formed by liquid immiscibility (i.e.,
aillikite, melilitite, nephelinite, basanite) can be explained
in terms of depth and degree of partial melting of the mantle.
Other more evolved rock types (e.g., syenites) may reflect
more extensive crystal fractionation prior to separation of
an immiscible carbonatite melt. Alternatively, extended
fractionation of evolved carbonated silicate magmas may
result in the formation of carbonatitic rocks from residual
melts, without immiscible separation of carbonate from
silicate melts. Within this broad spectrum of ‘carbon-
atitic’ rocks are the REE–F-rich carbonate rocks that may
319 O c tober 2021
 be precipitates from COH fluids. These rocks can be of
significant economic interest due to their enrichment in
REEs and other metals, such as Nb; however, formation of
these ores typically involves multiple stages of enrichment.
Experimental petrology has shown that primary carbon-
atite melts of alkali-rich, dolomitic to calcio-dolomitic
carbonate composition can be formed by low degrees of
partial melting of carbonate-bearing peridotite and eclogite
at pressures greater than about 2 GPa. But, because most
carbonatites are intrusive (plutonic) and were modified
by crystal accumulation from the primary melts, clear
evidence for a primary mantle origin may be absent.
Possibly as much as a quarter of known carbonatite occur-
rences are not associated with putative conjugate silicate
magmas (Woolley and Kjarsgaard 2008) and, therefore,
arguably do not present evidence of formation by liquid
immiscibility. Carbonatites without associated silicate
rocks and which carry mantle xenoliths and xenocrysts
have been inferred to be derived directly from the mantle
(Harmer and Gittins 1997), as per Figure 1.
Advances in in situ age determinations using the U–Pb
isotope system in perovskite and high-precision 40Ar/39Ar
and Sr–Nd–Hf–Pb and carbon and oxygen isotopic analyses
coupled with trace element analysis of mineral phases
continue to better define the temporal and chemical
relationships between coexisting carbonatite and silicate
rocks. For example, are the associated rocks cogenetic, or
comagmatic, or simply coeval? Isotope systematics also give
important information about the likely sources of melts
parental to carbonatites. They are also key to deciphering
the complex history of carbonatite-related ore deposits.
Such integrated studies are providing new insights into the
nature and origin of the diverse spectrum of carbonatites,
the role of carbonate in the mantle, and the sources of
carbon in carbonatites. Similarly, Ca isotopic compositions
of carbonatites (Amsellem et al. 2020) and chemical and
isotopic compositions of inclusions and their diamond host
(e.g., using O isotopes) (Timmerman et al. 2021 this issue)
are providing increasing evidence of recycling of crustal
carbonates during subduction into the deep, convecting
mantle as a major source of carbon in carbonatite rocks.
ACKNOWLEDGMENTS
BAK thanks the Geological Survey of Canada Targeted
Geoscience Initiative rare metal activity for support. We
thank Suzette Timmerman, Michael Anenburg and John
Eiler for comments on an earlier draft, and Richard Brooker
and Daniel Weidendorf for formal reviews. Jodi Rosso is
thanked for editorial work.

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