Kerimasi Volcano (Tanzania)

Lithos 238 (2015) 101119
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Lithos
journal homepage: www.elsevier.com/locate/lithos
Synthesis paper
A melt evolution model for Kerimasi volcano, Tanzania: Evidence from

carbonate melt inclusions in jacupirangite
Rka Kldos a, Tibor Guzmics a,, Roger H. Mitchell b, John Barry Dawson c, Ralf Milke d, Csaba Szab a
a
Lithosphere Fluid Research Laboratory, Institute of Geography and Earth Sciences, Etvs University Budapest, Pzmny Pter stny 1/C, Budapest 1117, Hungary
Lakehead University, Thunder Bay, ON P7B 5E1, Canada
School of Geosciences, University of Edinburgh, West Mains Road, Edinburgh EH9 3JW, United Kingdom
d
Free University Berlin, Habelschwerdter Allee 45, 14195 Berlin, Germany
b
c
a r t i c l e
i n f o
Article history:
Received 12 February 2015
Accepted 8 September 2015
Available online 21 September 2015
Keywords:
Carbonatite
Carbonate melt inclusion
Liquid immiscibility
Jacupirangite
Alkali carbonate
Kerimasi
a b s t r a c t
This study presents compositional data for a statistically signicant number (n = 180) of heated and quenched
(recreated) carbonate melt inclusions trapped in magnetite and clinopyroxene in jacupirangite from Kerimasi
volcano (Tanzania). On the basis of homogenization experiments for clinopyroxene-hosted melt inclusions
and forsteritemonticellitecalcite phase relations, a range of 1000 to 900 C is estimated for their crystallization
temperatures. Petrographic observations and geochemical data show that during jacupirangite crystallization, a
CaO-rich and alkali-poor carbonate melt (relative to Oldoinyo Lengai natrocarbonatite) existed and was
entrapped in the precipitating magnetite, forming primary melt inclusions, and was also enclosed in previously
crystallized clinopyroxene as secondary melt inclusions. The composition of the trapped carbonate melts in magnetite and clinopyroxene is very similar to the parental melt of Kerimasi calciocarbonatite; i.e., enriched in Na2O,
K2O, F, Cl and S, but depleted in SiO2 and P2O5 relative to carbonate melts entrapped at an earlier stage and higher
temperature (10501100 C) during the formation of Kerimasi afrikandite. Signicant compositional variation is
shown by the major minerals of Kerimasi plutonic rocks (afrikandite, jacupirangite and calciocarbonatite). Magnetite and clinopyroxene in the jacupirangite are typically transitional in composition between those of
afrikandite and calciocarbonatite. These data suggest that the jacupirangite represents an intermediate stage between the formation of afrikandite and calciocarbonatite. Jacupirangite most probably formed when immiscible
silicate and carbonate melts separated from the afrikandite body, although the carbonate melt was not separated
completely from the silicate melt fraction. In general, during the evolution of the carbonate melt at Kerimasi, concentrations of P2O5 and SiO2 decreased, whereas volatile content (alkalis, S, F, Cl and H2O) increased. Volatiles
were incorporated principally in nyerereite, shortite, burbankite, nahcolite and sulfohalite as identied by
Raman spectrometry. These extremely unstable minerals cannot be found in the bulk rock, because of alteration
by secondary processes. On the basis of these data, an evolutionary model is developed for Kerimasi plutonic
rocks.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Many petrologists consider that the bulk rock compositions of alkaline
silicate and associated carbonatite rocks cannot provide reliable information
regarding their parental magma compositions as they do not represent liquid compositions (Gittins and Harmer, 2003; Guzmics et al., 2012; Mitchell,
2009; Zurevinski and Mitchell, 2004). In contrast, studies of melt inclusions
in different host minerals have been used to obtain information about the
parental magma composition and its evolution (Andreeva, 2014; Bodnar
and Student, 2006; Guzmics et al., 2011, 2012; Kamenetsky and
Kamenetsky, 2010; Mitchell and Dawson, 2012; Roedder, 1979; Severs
Corresponding author.
E-mail address: tibor.guzmics@gmail.com (T. Guzmics).
http://dx.doi.org/10.1016/j.lithos.2015.09.011
0024-4937/ 2015 Elsevier B.V. All rights reserved.
et al., 2009; Sharygin et al., 2012; Solovova et al., 2006; Touret and
Frezzotti, 1993). Experimental studies of haplocarbonatites (Kjarsgaard,
1998; Lee and Wyllie, 1998b) and natural examples (Dawson et al., 1994;
Guzmics et al., 2012, 2015; Hay, 1983; Kjarsgaard and Peterson, 1991;
Kogarko et al., 1991; Le Bas, 1977; Nielsen et al., 1997; Panina, 2005;
Panina and Motorina, 2008; Romanchev and Sokolov, 1979; Solovova
et al., 1996) show that silicatecarbonate liquid immiscibility might play
an important role in genesis of many carbonatites. There is little information
available regarding the volatile and P2O5 contents of plutonic carbonate
melts, however they have a signicant role in trace element partitioning
during silicatecarbonate liquid immiscibility (Guzmics et al., 2015;
Martin et al., 2013; Veksler et al., 2012) and in characterization of their
physical properties (Mangler et al., 2014).
In this paper we present data for a statistically signicant number of
clinopyroxene- and magnetite-hosted carbonate melt inclusions and
102
R. Kldos et al. / Lithos 238 (2015) 101119
use these data to study the magmatic processes resulting in the formation of jacupirangite. In addition, on the basis of melt inclusion data, we
present an evolutionary model for the plutonic rocks of Kerimasi.
clinopyroxene and magnetite grains were polished and exposed in parafn oil mixed with 1 m sized Al2O3 powder without using any water in
order to avoid loss of water-soluble phases from the carbonate melt
inclusions.
Raman spectrometry was undertaken at ambient temperature at the
Faculty of Science Research and Instrument Core Facility of Etvs University Budapest (ELTE FS-RICF) using a Jobin-Yvon LabRAM HR (800 mm)
confocal Raman microspectrometer equipped with a frequency-doubled
Nd-YAG laser with an excitation wavelength of = 532 nm. During the
analyses, with a grating of 1800 lines/mm, the spectral resolution
remained under 1 cm1. The laser beam was focused with a 100
(N.A. = 0.9) objective. Raman measurements were performed on unheated carbonate melt inclusions in order to identify the minerals present. We
analyzed exposed and unexposed melt inclusions in clinopyroxenes and
exposed ones in magnetites. In the case of exposed melt inclusions we
did not remove the parafn oil from the sample to avoid alteration of
the water-soluble phases by air humidity. Oil did not affect the measurements as the Raman spectrum of parafn oil appears at clearly distinct
wavenumbers (peaks are at the region of 28502950 cm1) with respect
to the characteristic peaks of the minerals of interest (b1200 cm1).
Qualitative mineral identication and BSE imaging were undertaken
with 20 kV acceleration voltage and 10 nA current using an AMRAY1830I scanning electron microscope coupled with an EDAX EDS PV
9800 detector at Etvs University Budapest. Using a Linkam TS 1500
stage mounted on a Nikon Eclipse E600 polarization microscope (at ambient pressure), high temperature microthermometric experiments were
undertaken on clinopyroxene-hosted carbonate melt inclusions (n =
20). Heating temperatures varied between 850 and 1100 C. As magnetite
is not transparent in visible light, microthermometric experiments could
not be carried out on the magnetite-hosted melt inclusions.
2. Geological background
Jacupirangite xenoliths (34 cm) were collected by Professor J. B. Dawson
from volcanic agglomerates of the southern slopes of Kerimasi volcano.
Kerimasi is located 12 km from Oldoinyo Lengai in the Gregory Rift Valley
of Northern Tanzania (Fig. 1). Kerimasi is a stratovolcano, composed of nephelinitephonolitecarbonatite pyroclasts with nephelinite and carbonatite
tuffs and agglomerates (Church, 1995; Dawson, 2008; Mariano and Roeder,
1983). Plutonic rocks at Kerimasi (pyroxenite, ijolite, uncompahgrite,
afrikandite and calciocarbonatite) occur as xenoliths in the volcanic agglomerates (Church, 1995; Dawson, 2008; Guest, 1953; Guzmics et al., 2011, 2012).
Guzmics et al. (2011) and Zaitsev (2010) have reported nyerereite
as crystal inclusions in calciocarbonatite-hosted calcite. Guzmics et al.
(2011) found nahcolite in uid inclusions and carbonate melt inclusions
hosted in apatite and magnetite. Apatite- and magnetite-hosted carbonate melt inclusions show enrichment in Na2O + K2O (up to 28 wt.%)
(Guzmics et al., 2011, 2015). Mitchell (2015) observed NaCa carbonate
melt inclusions, whose compositions were similar to those of shortite,
hosted by primary calcite in Kerimasi calciocarbonatite. These observations indicate that Kerimasi might have erupted natrocarbonatite
magma similar to that occurring at Oldoinyo Lengai.
3. Sample preparation and analytical methods
All samples were prepared for analysis at the Lithosphere Fluid Research Laboratory, Etvs University Budapest. Heated and unheated
Pyroclasts of Oldoinyo Lengai

LOOLMURWAK
debris flow
LOLUNI
fine-bedded carbonatite tuff
massive bedded carbonatite tuff

250 S
P
Basalt
carbonatite tuff-pisolithic facies

calcite cemented sovite breccia
nephelinitic tuffs and agglomerates
sovite
KERIMASI
P
PP
crater
A
fault
Basalt
sampling area
cross-section
B
0
8
km
Diagrammatic cross-section
36E
Fig. 1. Schematic geological map of Kerimasi volcano (Tanzania) and a diagrammatic cross-section of Kerimasi. Red circles show the sample collection localities. (For interpretation of the
references to color in this gure legend, the reader is referred to the web version of this article.)
Modied from Dawson (2008).
103
For the heating and quenching experiments a furnace technique was

used for 300 separated magnetite and clinopyroxene grains encapsulated in graphite containers in the Lithosphere Fluid Research Laboratory,
Etvs University Budapest. A Carl-Zeiss Jena high temperature and
1 atm furnace was used for heating with diverse temperatures between
850 C and 950 C to produce homogeneous melts in the inclusions. The
uncertainty in the temperature of the furnace was 15 C at 1000 C.
Quenching rates were 300350 C/s.
One hundred and eighty quenched carbonate melt inclusions were
exposed using parafn oil mixed with 1 m Al2O3 powder, and their
composition together with those of the minerals of the rock were determined using a wavelength dispersive (WDS) JEOL JXA 8200 Superprobe,
equipped with ve crystal spectrometers at the Free University Berlin.
Acceleration voltage was 15 kV and beam current 10 nA for all phases
analyzed. A defocused 25 m beam diameter was used for quenched
melts and mica. Sodium was measured in the rst 5 s of analysis in
order to minimize uncertainty due to volatilization.
spectra, crystal inclusions are typically rock-forming minerals i.e., magnetite, calcite, apatite, mica and olivine (Figs. 3A and G, 4A). Melilite and
nepheline can be observed as small (b 20 m) crystal inclusions only in
clinopyroxenes (Fig. 4A).
Melt inclusions in magnetite are randomly distributed and contain
apatite, calcite, dolomite, mica, burbankite, alkali carbonates, sulfate
and hydrocarbonate (Fig. 3EF, Fig. 4). Clinopyroxene-hosted melt inclusions are located along healed fractures (Fig. 3B) and consist of magnetite, apatite, calcite, dolomite, mica, burbankite, alkali carbonates,
sulfate and hydrocarbonate (Fig. 3GH, Fig. 4). Baddeleyite, zirconolite,
perovskite and olivine are found very rarely in the melt inclusions of
both magnetite and clinopyroxene. Identication of these minerals
was based on EDS and Raman spectra (see next section). Bubbles cannot
be observed in the melt inclusions at room temperature. Fluid inclusions
are not found in rock-forming minerals. Apatite typically contains
phlogopite crystal inclusions, which are richer in F than those hosted
by magnetite and clinopyroxene.
4. Petrography
5. Results
The jacupirangite has a hypidiomorphic granular texture, and consists dominantly of euhedral to subhedral (10600 m) green (both in
macroscopic and stereo microscopic views) clinopyroxene (~ 6070
vol.%) and magnetite (153000 m) (~2030 vol.%) (Fig. 2A). Located
between the clinopyroxene and magnetite crystals there is an interstitial microcrystalline assemblage of subhedral calcite (10200 m),
subhedral to anhedral magnetite (550 m), apatite (545 m), mica
(1080 m), olivine (10100 m) and trace amounts of pyrite (Fig. 2B
and C). This interstitial mineral association resembles the mineral assemblage of Kerimasi calciocarbonatite (Guzmics et al., 2011).
Clinopyroxene and magnetite contain crystal inclusions and 550 m irregularly shaped melt inclusions (Fig. 3). On the basis of EDS and Raman
5.1. High resolution Raman microspectrometry

The principal objective of the Raman spectrometry was to identify
alkali carbonates and other water-soluble and/or very small (12 m)
unexposed phases in the unheated clinopyroxene- and magnetitehosted melt inclusions (Fig. 4B). It should be noted that substitution
schemes in alkali carbonates such as nyerereite and shortite (e.g.,
SO2
K+ Na+, Ca2+ Sr2+/Ba2+, CO2
3
4 ) can result in a shift of
Raman peaks (Zaitsev, 2010). Alkali carbonates are identied as pure
end-members following Zaitsev (2010) and Zaitsev and
Chakhmouradian (2002). In both clinopyroxene- and magnetitehosted carbonate melt inclusions nyerereite [Na2Ca(CO3)2], shortite
Fo
BFo
Cpx
Cpx
Cpx
Cpx
Mgt
Mgt
Cpx
Phl
Cpx
Mgt
Cpx
Cc
Phl
Cpx
Ap
Fo
Cpx
Mgt
2 mm
200 m
Cpx
Cpx
Mgt
Cc
Fo
Cpx
Ap
Cpx
200 m
Fig. 2. Texture of Kerimasi jacupirangite, illustrating large clinopyroxene and magnetite crystals and a microcrystalline interstitial assemblage of calcite, magnetite, apatite, phlogopite and
forsterite. Cpx: clinopyroxene; Mgt: magnetite; Cc: calcite; Fo: forsterite; Phl: phlogopite; Ap: apatite. (A) Photomicrograph, stereomicroscope, (BC) back-scattered electron image.
104
Mgt
Cc
Cpx
Cc
Cpx
Cpx
Ap
Mgt
Ap
Mgt
Cpx
Ap
Cpx
Cpx
Cpx
Ap
Ca-Na-K
carb
MI
50 m
500 m
Cpx
Cpx
melt
inclusion
melt
inclusion
10 m
Mgt
Bad
10 m
F
Bad
Ap
Cc
K
aN
a- rb
C ca
Prv
hole
Mgt
20 m
Ca-Na-K
carb
20 m
Cpx
Bad
Ap
hole
Cc
hole
Phl
Phl
Cpx
50 m
hole
Ca-Na-K
carb
Mgt
Ap
20 m
Fig. 3. Magnetite- and clinopyroxene-hosted carbonate melt inclusions in Kerimasi

jacupirangite. MI: melt inclusion; Cpx: clinopyroxene; Mgt: magnetite; Cc: calcite; Phl:
phlogopite; Ap: apatite; Prv: perovskite; Bad: baddeleyite; CaNaK: carb alkali carbonate.
Holes indicate former uid phases that existed in the melt inclusion prior to exposure.
(A) Randomly distributed, primary carbonate melt inclusions in magnetite; backscattered electron image. (B) Clinopyroxene-hosted secondary carbonate melt inclusions
occurring along healed fractures; photomicrograph, transmitted light, 1 N. (C, D). Unexposed secondary carbonate melt inclusions in clinopyroxene; photomicrograph, transmitted light, 1 N. (E, F). Mineral phases in exposed primary carbonate melt inclusions in
magnetite; back-scattered electron image. (G, H). Mineral phases in exposed
clinopyroxene-hosted carbonate melt inclusions; back-scattered electron image.
[Na2Ca2(CO3)3], calcite (CaCO3), burbankite [(Na,Ca)3(Sr,Ba,Ce)3(CO3)5]

and dolomite [CaMg(CO3)2] were identied (Figs. 3EH, 4B).
Hydrocarbonates such as nahcolite (NaHCO3) and sulfate as sulfohalite
[Na6(SO4)2FCl] were detected in the melt inclusions although these
are not as common as the above phases (Fig. 4B).
5.2. High temperature microthermometry and heatingquenching experiments by the furnace technique
During our high temperature microthermometry on clinopyroxenehosted carbonate melt inclusions, homogenization of the inclusions
(n = 14) was observed between 850 and 1000 C with the
homogenization of the uid bubble into the melt phase. At the homogenization temperature only a carbonate melt phase was present inside
the melt inclusions, however in some experiments a solid phase
remained after uid-melt homogenization. A representative homogenization experiment is shown in Fig. 5. First visible melting began at
350 C (not shown). At 780 C the uid phase was a globular bubble
in the melt phase (Fig. 5A). On further heating, size of the uid phase decreased signicantly (Fig. 5B). Disappearance of the uid bubble occurred at 992 C (Fig. 5C). Complete uid-melt homogenization was
indicated by pop-back of the uid bubble into the melt phase during
cooling (Fig. 5D). Minimum homogenization temperature was measured as 850 C.
For the heatingquenching experiments, we separated 150 grains
each of clinopyroxene and magnetite. We applied the minimum homogenization temperature (850 C), observed in microthermometric
measurements, for heating the clinopyroxene-hosted melt inclusions
in the furnace. In the case of magnetites we applied 950 C, based on
the results of our previous melt inclusion studies (Guzmics et al.,
2011, 2012). All quenched carbonate melts were homogeneous
(Fig. 6). In addition to the recreation of melt phase(s) at entrapment,
the furnace technique was also important for the recognition of accidentally entrapped minerals in the melt inclusions. This implies that host
minerals, magnetite and clinopyroxene, entrap the melt phase together
with any other minerals precipitated from the melt (e.g., Danyushevsky
et al., 2002; De Vivo and Bodnar, 2003; Frezzotti, 2001; Guzmics et al.,
2008a; Kent, 2008; Mitchell, 2009; Roedder, 1984, 1987; Schiano,
2003; Zajacz et al., 2008). In the quenched clinopyroxene- and
magnetite-hosted carbonate melt inclusions accidentally trapped
mineral(s) were rarely observed (e.g., calcite and/or apatite, perovskite,
olivine and/or mica). In one case zirconolite (Fig. 6B) and baddeleyite
(not shown) have also been found in the magnetite-hosted carbonate
melt inclusions.
Spherical cavities (Fig. 6) indicated that a uid phase was present
before opening the inclusions. This is consistent with the experimental
studies of Brooker and Kjarsgaard (2011) and our microthermometric
observations that quenching of dissolved uid into the carbonate melt
phase is not possible. We also carried out Raman analyses focusing the
laser spot into the bubble phases of the heated (800950 C) melt inclusions, however we only detected small peaks of CO2 (~ 1284 cm1,
1387 cm1) suggesting that this phase is a relatively low density CO2dominated uid.
5.3. Compositions of the rock-forming minerals

The major element compositions of magnetite and clinopyroxene
are shown in Tables 1 and 2. The magnetite is a solid solution of
sensu stricto magnetite (Fe3O4), magnesioferrite (MgFe2O4) and
jacobsite (MnFe2O4) together with lesser amounts of ulvspinel
(Fe2TiO4) and spinel (MgAl2O4). Magnetite contains small quantities
of TiO2 (average 2.5 wt.%) and Al2O3 (average 1.3 wt.%). Cr2O3 contents
were below the detection limit (0.06 wt.%). Clinopyroxene is diopside
and contains MgO (15.417.9 wt.%) and CaO (24.025.1 wt.%), with
low Al2O3 (average 0.5 wt.%) and TiO2 (average 0.1 wt.%) contents.
FeOT varies between 1.6 and 4.9 wt.%. Clinopyroxene compositions
can be expressed in terms of the end-members: diopside (CaMgSi2O6 =
84.896.8 mol%); hedenbergite (CaFeSi2O6 = 0.012.6 mol%); aegirine
(NaFeSi2O6 = 0.02.9 mol%) (Fig. 7); Ca-Tschermak's (CaAlAlSiO6 =
0.01.9 mol%); Fe-Tschermak's (CaFeAlSiO6 = 0.04.1 mol%); ferrosilite
(Fe2Si2O6 = 0.02.9 mol%) and wollastonite (Ca2Si2O6 = 0.01.2 mol%)
(Table 2). All compositions are given in the electronic supplement. Apatites are uorapatites with SiO2 contents of 0.21.2 wt.% (Table 3). Olivine is forsterite (Fo8397, mg# = 0.870.97) with high MgO (44.6
54.4 wt.%) and low FeO (3.011.9 wt.%) and MnO (0.24.0 wt.%)
(Table 4). Mica is phlogopite and contains 3.24.7 wt.% FeOT and an average of 0.3 wt.% TiO2. Fluorine varies between 0.9 and 2.3 wt.%
Rock-forming mineral phases

T=25C
clinopyroxene
665
clinopyroxene
633
923
Melilite
105
963
Mineral phases in
melt inclusions
Apatite
T=25C
1055
855
1002
100
190
633
Phlogopite
278 342
Sulfohalite
1126
677
1055
591 605
Apatite
1078
430
1086
Calcite
153
280
712
820
426
854
Forsterite
915 956
539
Intensity (arbitrary unit)
Intensity (arbitrary unit)
963
659
646
Shortite
Burbankite
Nyerereite
1080
1087
1073
712
1097
Magnetite
324
722
665
353 389
322
138
164 228
766
400
500
Dolomite
1013
556
300
1091
1072
684
594
200
1045
697
707
100
Nahcolite
685
1045
854
1086
Clinopyroxene
Calcite
711
600
700
800
900
1000 1100
600
-1
700
800
900
1000
1100
1200
-1
Raman shift (cm )
Raman shift (cm )
Fig. 4. Raman spectra of (A) rock-forming minerals and (B) characteristic mineral phases found in the carbonate melt inclusions. Nyerereite, shortite, burbankite, nahcolite and sulfohalite
can be found only in the melt inclusions. Arrows indicate the characteristic Raman peaks. Peak positions were determined by tting to a GaussianLorentzian function.
780C
900C
carbonate melt
carbonate melt
Cpx
992C
homogenization
10 m
Cpx
870C
carbonate melt
bubble
pops-back
10 m
quenched
carbonate melt
Cpx
10 m
carbonate melt
zirconolite
bubble
decreases
bubble
appears
10 m
quenched
carbonate melt
Cpx
Mgt
20 m
Mgt
cavity
20 m
quenched
carbonate melt
Cpx
cavity
50 m
Fig. 5. Microthermometric homogenization experiment of clinopyroxene-hosted carbonate

melt inclusion shown from 780 C. At 780 C the uid phase appeared in the melt phase
(A). On further heating, the size of uid phase continuously decreased (B). Disappearance
of the uid bubble occurred at 992 C (C). Complete uid-melt homogenization was indicated by pop-back of the uid bubble into the melt phase during cooling (D). Photomicrographs.
Cpx: clinopyroxene.
Fig. 6. Characteristic magnetite- (A, B) and clinopyroxene-hosted (C) quenched carbonate

melt inclusions after heating to 950 and 850 C, respectively. Picture B shows an accidentally entrapped zirconolite. Back-scattered electron images. Presence of cavities indicates
that former uid phases existed in the melt inclusions before exposure. Mgt: magnetite;
Cpx: clinopyroxene.
106
Table 1
Representative compositions of magnetite in wt.%, Kerimasi jacupirangite, Tanzania.
0.98
0.69
84.22
0.52
6.59
93.00
TiO2
Al2O3
FeOT
MnO
MgO
Total
2.17
0.62
84.56
3.20
2.85
93.41
2.51
1.05
84.59
2.45
2.93
93.54
3.27
1.37
83.50
2.37
3.20
93.71
4.38
1.86
81.53
2.42
3.71
93.90
3.37
1.57
82.98
2.53
3.29
93.73
2.55
1.47
83.65
2.70
3.21
93.57
1.56
0.45
85.73
2.77
2.77
93.27
1.77
0.57
85.88
2.43
2.67
93.32
1.70
0.61
86.22
2.08
2.73
93.34
Average
n = 42
1SD
Min
Max
2.49
1.28
83.75
2.60
3.40
1.12
0.90
1.77
0.51
0.99
0.39
0.11
80.75
0.52
2.53
4.57
3.60
86.64
3.52
8.21
Formula based on 3 cations and 4 oxygens

Ti
Al
Fe3+
Fe2+
Mn
Mg
Cation sum
0.027
0.030
1.916
0.652
0.016
0.359
3.000
0.061
0.027
1.850
0.800
0.102
0.159
3.000
0.071
0.046
1.813
0.830
0.078
0.163
3.000
0.091
0.060
1.757
0.839
0.075
0.177
3.000
0.122
0.081
1.676
0.842
0.076
0.204
3.000
0.094
0.068
1.743
0.833
0.080
0.182
3.000
0.071
0.064
1.793
0.809
0.085
0.178
3.000
End-members (mol.%)
Sp
Mgf
Usp
Mgt
Jac
1.50
34.40
2.70
59.80
1.60
1.35
14.56
6.10
67.78
10.21
2.30
14.00
7.10
68.80
7.80
3.00
14.71
9.10
65.68
7.50
4.05
16.34
12.19
59.82
7.60
3.40
14.81
9.40
64.38
8.00
3.20
14.61
7.10
66.58
8.50
1.00
14.50
4.40
71.30
8.80
1.25
13.75
5.00
72.30
7.70
1.35
13.95
4.80
73.30
6.60
0.044
0.020
1.892
0.801
0.088
0.155
3.000
0.050
0.025
1.875
0.823
0.077
0.150
3.000
0.048
0.027
1.877
0.829
0.066
0.153
3.000
Average
n = 42
1SD
Min
Max
2.77
16.01
6.82
66.22
8.17
1.93
5.50
2.96
5.27
1.65
0.25
11.65
1.10
45.63
1.60
7.75
43.63
12.51
74.79
11.09
FeOT all Fe expressed as FeO, 1SD one absolute standard deviation; major element composition of all the studied 42 magnetites can be followed as an electronic supplement. Spspinel,
Mgfmagnesioferrite, Uspulvospinel; Mgtmagnetite, Jacjacobsite.
(Table 5). Calcite contains an average of 0.3 wt.% FeOT and SrO, 0.7 wt.%
MgO, whereas MnO is below the detection limit.
Na2O + K2O) carbonate melt physically separated and crystallized leading to the formation of the calciocarbonatite body.
5.4. Major element composition of quenched melts
6.1. Jacupirangite mineral compositions comparison with Kerimasi

afrikandite and calciocarbonatite
Representative major element compositions of the quenched carbonate melts are shown in Tables 6 and 7. Compositions of all the
quenched melt inclusions (n = 180) can be found as an electronic supplement. Both magnetite- and clinopyroxene-hosted melts are principally P-, F- and S-bearing, CaNaK-rich carbonate compositions. With
increasing content of Na2O, CaO shows a decreasing trend in all carbonate melts (Fig. 8A). The total alkali (Na2O + K2O) content of magnetitehosted carbonate melt inclusions is 14.7 wt.%, whereas clinopyroxenehosted ones contain 16.5 wt.% on average. Small but signicant amounts
of SiO2 (average 0.6 wt.%) are also present in all of the carbonate melts.
Generally, magnetite-hosted carbonate melts have relatively higher
P2O5 (average 1.7 wt.%) and F (average 0.7 wt.%) content than those in
clinopyroxenes (averages 1.4 wt.% and 0.4 wt.%, respectively). A correlation between P2O5/Na2O and CaO/Na2O exists (Fig. 8B). The majority of
the carbonate melts also contain small, but signicant amounts of SrO
(average 0.4 wt.%), BaO (average 0.3 wt.%) and SO3, the latter have a
higher concentration in clinopyroxene-hosted carbonate melts (average 0.7 wt.%) relative to those in magnetite (average 0.4 wt.%).
6. Discussion
To understand the genesis and evolution of jacupirangite at
Kerimasi, it is necessary to consider the petrogenetically associated
rocks (Dawson, 2008, 2012; Dawson and Smith, 1992; Guzmics et al.,
2012; Le Bas, 1977; Mitchell, 2005). Previous investigations of Kerimasi
plutonic rocks (calciocarbonatite and afrikandite) including melt inclusion studies, were undertaken by Guzmics et al. (2011, 2012). On the
basis of these studies, it was determined that the formation and evolution of afrikandite and calciocarbonatite are closely related as the parental melt of the calciocarbonatite is possibly the result of silicate
carbonate liquid immiscibility, occurring during the formation of
afrikandite. Subsequent to this silicatecarbonate liquid immiscibility,
a CaO-rich (3343 wt.%) and alkali-poor (at least 710 wt.% of
The compositional variation of clinopyroxenes can reect compositional changes in their parent melt (Eriksson, 1989; Green and
Pearson, 1985; Le Bas, 1962, 1987; Lima, 2000; Mitchell, 1980; Nisbet
and Pearce, 1977). On the basis of data given by Guzmics et al. (2012),
the brown cores of clinopyroxenes in the afrikandite began to crystallize
(at 11001150 C) from a carbonated melilitenephelinite melt that
was strongly undersaturated in silica (SiO2 = 4043 wt.%) relative to
basalts (SiO2 = 4756 wt.%, e.g. Kamenetsky et al., 2001). Perovskite
precipitation from this low-siliceous melt indicates a low activity of
SiO2 (log a SiO2 b ~ 0.8 at 1150 C) based on the reaction: CaTiO3
(perovskite) + SiO2 = CaTiSiO5 (sphene) (Carmichael et al., 1970;
Smith, 1970; Veksler and Teptelev, 1990). Sphene is absent in Kerimasi
afrikandite (Guzmics et al., 2012).
Partitioning of Al (and Ti) into clinopyroxene coexisting with silicate
melt is a function of silica activity as the following simplied reaction illustrates: CaAlAlSiO6 (Ca-Tschermak's component) + SiO2 =
CaAl2Si3O8 (plagioclase), which requires an increase in the Tschermak's
component (Ts) of clinopyroxene with decreasing silica activity for a
given plagioclase composition (Verhoogen, 1962; Carmichael et al.,
1970). However, at low SiO2 activity (e.g., below to perovskitesphene
reaction curve) melilite is stable instead of plagioclase (Carmichael
et al., 1970), resulting in a decrease in the Tschermak's component of
clinopyroxene, co-precipitated with melilite, with decreasing silica activity (Carmichael et al., 1970). Based on data given by Guzmics et al.
(2012), the brown clinopyroxene cores in afrikandite are signicantly
higher in CaTs + FeTs [CaAlAlSiO6 + CaFeAlSiO6] (8.911.0 mol%) relative to their green rims (0.14.3 mol%) and to clinopyroxenes in
jacupirangite (0.04.1 mol%, Table 2). This observation can be explained
by the fractionation of nepheline, perovskite, magnetite and melilite
during afrikandite formation (Guzmics et al., 2012). Fractionation of
these minerals results in a decrease in the Al and Ti contents of the
melt (Guzmics et al., 2012) and eventually diminished Al, Ti, and
107
Table 2
Representative compositions of clinopyroxene in wt.%, Kerimasi jacupirangite, Tanzania.
SiO2
TiO2
Al2O3
Cr2O3
FeOT
MnO
MgO
CaO
Na2O
K2O
Total
54.00
0.14
0.47
0.00
4.04
0.39
15.89
24.96
0.00
0.20
100.08
54.86
0.07
0.46
0.00
2.14
0.23
17.63
24.80
0.15
0.00
100.35
54.44
0.25
0.81
0.02
3.91
0.34
15.94
24.04
0.32
0.00
100.08
54.66
0.05
0.22
0.00
3.84
0.59
16.17
24.69
0.16
0.02
100.41
54.55
0.11
0.18
0.00
3.72
0.48
16.37
24.46
0.23
0.00
100.09
54.78
0.07
0.22
0.00
3.59
0.34
16.43
24.66
0.18
0.00
100.28
54.60
0.04
0.23
0.00
3.75
0.56
16.37
24.59
0.21
0.01
100.38
54.33
0.12
0.32
0.00
4.06
0.56
16.06
24.45
0.28
0.01
100.19
54.54
0.08
0.47
0.02
3.31
0.32
16.46
24.59
0.26
0.00
100.06
54.16
0.09
0.67
0.00
4.05
0.38
16.25
24.42
0.21
0.01
100.25
Average
n = 67
1SD
Min
Max
54.41
0.14
0.52
0.01
3.46
0.39
16.47
24.54
0.24
0.02
0.50
0.08
0.33
0.01
0.91
0.09
0.67
0.24
0.08
0.03
53.16
0.03
0.00
0.00
1.63
0.22
15.43
24.04
0.00
0.00
55.43
0.30
1.37
0.05
4.98
0.71
17.86
25.09
0.44
0.20

Si
Ti
Al(IV)
Al(VI)
Cr
Fe3+
Fe2+
Mn
Mg
Ca
Na
K
Cation sum
1.981
0.004
0.019
0.001
0.000
0.010
0.114
0.012
0.869
0.981
0.000
0.009
4.000
1.984
0.002
0.016
0.004
0.000
0.018
0.046
0.007
0.951
0.961
0.011
0.000
4.000
1.992
0.007
0.008
0.027
0.001
0.000
0.120
0.011
0.870
0.943
0.023
0.000
4.000
1.996
0.001
0.004
0.005
0.000
0.007
0.110
0.018
0.880
0.965
0.011
0.001
4.000
1.994
0.003
0.006
0.002
0.000
0.014
0.099
0.015
0.892
0.958
0.016
0.000
4.000
1.998
0.002
0.002
0.008
0.000
0.002
0.107
0.010
0.894
0.964
0.013
0.000
4.000
1.991
0.001
0.009
0.001
0.000
0.021
0.093
0.017
0.890
0.961
0.015
0.000
4.000
1.987
0.003
0.013
0.001
0.000
0.025
0.099
0.017
0.876
0.958
0.020
0.001
4.000
1.990
0.002
0.010
0.011
0.001
0.012
0.089
0.010
0.896
0.961
0.018
0.000
4.000
1.978
0.002
0.022
0.007
0.000
0.026
0.097
0.012
0.885
0.955
0.015
0.001
4.000
mg#
0.88
0.95
0.88
0.89
0.90
0.89
0.90
0.90
0.91
0.90
End-members (mol.%)
Ae
Jd
FeTs
AlTs
Di
Hd
En
Fe
Wo
FeTs + AlTs
Ae
Di
Hd
0.00
89.61
10.39
0.00
0.00
1.04
0.12
87.99
10.21
0.00
0.65
0.00
1.16
1.07
0.00
0.79
0.41
95.32
0.00
0.10
2.32
0.00
1.20
1.11
98.89
0.00
0.00
2.31
0.00
0.44
87.79
6.86
0.00
2.61
0.00
0.44
0.00
92.75
7.25
0.74
0.39
0.00
0.14
88.93
8.48
0.00
1.31
0.00
0.14
0.76
90.60
8.64
1.44
0.21
0.00
0.00
90.02
6.64
0.00
1.69
0.00
0.00
1.47
91.77
6.77
0.23
0.82
0.00
0.00
90.03
7.05
0.00
1.88
0.00
0.00
1.53
0.00
0.59
0.10
89.85
6.45
0.00
1.49
0.00
0.68
0.23
92.52
7.25
2.01
0.00
0.53
0.08
88.52
7.70
0.00
1.16
0.00
0.62
1.56
91.85
6.59
1.23
0.63
0.00
0.45
90.18
6.11
0.00
1.41
0.00
0.45
2.05
90.12
7.84
1.52
0.00
1.12
0.66
89.12
5.34
0.00
2.24
0.00
1.78
1.26
92.47
6.27
Min
0.85
Max
0.96
Average
n = 67
1SD
Min
Max
1.32
0.35
0.60
0.32
90.27
5.47
0.01
1.64
0.02
0.92
0.86
0.58
0.94
0.40
3.22
3.14
0.08
0.66
0.15
1.02
0.00
0.00
0.00
0.00
84.83
0.00
0.00
0.00
0.00
0.00
2.87
2.31
4.10
1.90
96.79
12.63
0.48
2.94
1.23
4.14
1.58
92.86
5.56
1.36
93.01
5.63
0.89
3.41
3.22
FeOT all Fe expressed as FeO, 1SD one absolute standard deviation, mg# = Mg/(Mg + Fe2+), major element composition of all the studied 67 clinopyroxenes can be followed as an electronic supplement. Aeaegirine, Jdjadeite, TsTschermak's component, Didiopside, Hdhedenbergite, Feferrosilite, Wowollastonite.
Tschermak's content of co-precipitated clinopyroxene (Carmichael

et al., 1970).
Thus, a continuous compositional transition can be seen from brown
cores through green rims of clinopyroxenes of afrikandite into green
clinopyroxenes of jacupirangite as shown on SiO2MgO, TiO2FeOT, and
TiO2Al2O3 diagrams (Fig. 9). The majority of the clinopyroxenes in
jacupirangite contain no detectable Al2O3 and less than 0.05 wt.% TiO2
(Fig. 9, Table 2). Similar data for clinopyroxenes from Kerimasi have
been published (Church, 1995) and for other alkaline silicatecarbonatite
complexes (Donaldson and Dawson, 1978; Le Bas, 1977; Peterson, 1989;
Rubie and Le Bas, 1977; Simonetti and Bell, 1994). The green rims of
afrikandite clinopyroxenes have crystallized from a silicate melt that
was depleted in FeOT, Al2O3 and TiO2, but enriched in MgO. The enrichment in MgO and depletion in FeOT, Al2O3 and TiO2 of the clinopyroxenes
(Fig. 9) follow the melt evolution trend observed during afrikandite formation (Guzmics et al., 2012). Fig. 9 shows that clinopyroxenes in
jacupirangite started to crystallize with the same composition (Ti, Al, Si,
Mg and Fe) as afrikandite clinopyroxenes. The latter coexisted with immiscible silicatecarbonate melts in perovskite-hosted melt inclusion
and formed green rims. These observations suggest a consanguineous
relationship between afrikandite and jacupirangite. Overall the Kerimasi

clinopyroxenes are considered as unevolved, as they are enriched in diopside and hedenbergite and poor in aegirine compared to clinopyroxenes
occurring in ijolites, urtites and calcite carbonatites in diverse alkaline silicatecarbonatite complexes (Fig. 7), suggesting that Kerimasi afrikandite
and jacupirangite pyroxenes represent relatively early precipitates.
Comparing the compositions of magnetites from afrikandite,
jacupirangite and calciocarbonatite, a compositional evolution can also
be seen (Fig. 10). Jacupirangite magnetites are depleted in TiO2, Al2O3
and Cr2O3 and enriched in FeOT in common with magnetites in
calciocarbonatite (Fig. 10). In contrast, magnetites in afrikandite have a
higher TiO2 (Fig. 10) and Cr2O3 contents. The correspondence of the composition of magnetites in jacupirangite and calciocarbonatite together
with the presence of similar carbonate melt inclusions suggests that
these minerals crystallized from a similar carbonate melt (Fig. 10). Magnetites in afrikandite were formed during silicatecarbonate liquid immiscibility (Guzmics et al., 2012). During immiscibility of the silicate
and carbonate melts, Ti and Al strongly partition into the silicate relative
to carbonate melt (Guzmics et al., 2012, 2015; Jones et al., 1995;
Kjarsgaard, 1998; Martin et al., 2012, 2013; Mitchell, 2009; Veksler
108

jacupirangite (Kerimasi), this study
afrikandite cpx rim (Kerimasi), Guzmics et al. 2012
afrikandite cpx core (Kerimasi), Guzmics et al. 2012
afrikandite (Kerimasi), Church, 1995
uncompahgrite (Kerimasi), Church, 1995
Aegirine
melilite nephelinite (Kerimasi), Church, 1995
80
ijolite (Kerimasi), Church, 1995
20
calcite carbonatite (Aley) Reguir et al. 2012

calcite carbonatite (Murun) Reguir et al. 2012
calcite carbonatite (Ozernaya Varaka) Reguir et al. 2012
40
mo
Ae
clinopyroxene-apatite-calcite carbonatite (Eden Lake) Reguir et al. 2012
60
phlogopite-clinopyroxene-calcite carbonatite (Aln) Reguir et al. 2012

amphibole-diopside-calcite silicocarbonatite (Afrikanda) Reguir et al. 2012
Hd
mo
l. %
l. %
andradite-diopside-calcite silicocarbonatite (Oka) Reguir et al. 2012
40
clinopyroxene-calcite carbonatite (Ozernyi) Reguir et al. 2012

diopside-calcite silicocarbonatite (Prairie Lake) Reguir et al. 2012
60
phlogopite-diopside-calcite carbonatite (Turiy Mys) Reguir et al. 2012

damtjernite (Al-Na diopside) (Fen complex), Mitchell, 1980
damtjernite (Ti-Al salite) (Fen complex), Mitchell, 1980
20
80
vibetoite (Fen complex), Mitchell, 1980

ijolite (Fen complex), Mitchell, 1980
melanite ijolite (Fen complex), Mitchell, 1980
silicocarbonatite (Fen complex), Mitchell, 1980
urtite (Fen complex), Mitchell, 1980
Diopside
80
60
40
20
mol. % Di
Hedenbergite
Fig. 7. Compositions of jacupirangite clinopyroxenes (mol.%), expressed as diopside (CaMgSi2O6), hedenbergite (CaFeSi2O6) and aegirine (NaFeSi2O6) compared to those of clinopyroxenes
in other alkaline complexes. This gure demonstrates that Kerimasi clinopyroxenes have relatively unevolved compositions compared to clinopyroxenes from more differentiated rocks
such as ijolites, urtites and calcite carbonatites.
Data are from this study, Church (1995); Guzmics et al. (2012); Mitchell (1980) and Reguir et al. (2012).
et al., 1998) resulting in a carbonate melt extremely depleted in these elements (Guzmics et al., 2011, 2015). Hence, magnetites crystallizing from
the physically separated carbonate melt at lower temperature (800
900 C), probably would have lower Ti and Al contents than those,
which had been formed before the separation of silicate and carbonate
melts at higher temperature (10501100 C). Nevertheless, the rims of
magnetites in calciocarbonatite are signicantly enriched in MgO and
Al2O3, due to extreme fractionation together with advanced oxidation of
the carbonate melt during the nal stages of magma evolution
(Guzmics et al., 2015) (Fig. 10 in this study). At Kerimasi, in carbonatite
tuff and lapilli Reguir et al. (2008) have found TiO2-rich (up to 10 wt.%)
and MgO-poor (56 wt.%) magnetites, which differ from the great majority of magnetites, which are TiO2-poor (b 5 wt.%) (Fig. 10).
Forsterite (Table 4) is a common mineral in calciocarbonatites
(Andreeva, 2014; Panina, 2005; Panina and Stoppa, 2009) whereas,
monticellite is less abundant (Guzmics et al., 2011). In the Kerimasi
jacupirangite, olivines are forsteritic (Fo8397) (Fig. 11A) and lack
monticellite rims. In contrast the calciocarbonatite contains
monticellites with forsteritic (Fo9596) cores (Fig. 11B), suggesting earlier crystallization of the jacupirangite relative to the calciocarbonatite.
Phlogopite in jacupirangite and calciocarbonatite are both F-rich.
The F-rich character of phlogopites from the carbonatites can be partly
Table 3
Representative compositions of apatite in wt.%, Kerimasi jacupirangite, Tanzania.
SiO2
MnO
SrO
CaO
Na2O
P2O5
F
Cl
Total
O = (F,Cl)2
Total
0.94
0.03
0.20
57.00
0.07
39.63
1.96
0.01
99.84
0.83
99.02
1.17
0.05
0.05
55.50
0.13
39.49
3.24
0.01
99.63
1.37
98.27
1.16
0.00
0.16
56.91
0.12
39.56
1.88
0.01
99.80
0.79
99.01
1.13
0.02
0.23
57.10
0.14
39.41
1.79
0.01
99.81
0.76
99.06
0.57
0.06
0.09
55.88
0.07
39.38
3.39
0.01
99.45
1.43
98.02
0.75
0.00
0.05
56.03
0.07
39.86
2.70
0.00
99.46
1.14
98.32
0.25
0.02
0.10
55.93
0.10
39.88
3.04
0.00
99.32
1.28
98.03
0.55
0.01
0.05
55.74
0.07
39.71
3.00
0.00
99.13
1.26
97.86
0.56
0.03
0.06
56.00
0.10
39.80
2.93
0.02
99.49
1.24
98.26
0.83
0.04
0.00
56.12
0.09
39.44
2.90
0.00
99.44
1.22
98.21
Average
n = 11
1SD
Min
Max
0.77
0.03
0.09
56.20
0.09
39.69
2.67
0.01
0.29
0.02
0.07
0.52
0.03
0.28
0.53
0.00
0.25
0.00
0.00
55.50
0.06
39.38
1.79
0.00
1.17
0.06
0.23
57.10
0.14
40.39
3.39
0.02
Formula based on 16 cations and 25 anions (O, F, Cl)

Si
Mn
Sr
Ca
Na
P
F
Cl
Cation sum
0.148
0.005
0.007
9.581
0.022
5.264
0.972
0.003
16.000
1SD one absolute standard deviation.
0.179
0.006
0.002
9.093
0.039
5.113
1.565
0.003
16.000
0.182
0.000
0.014
9.572
0.037
5.259
0.933
0.002
16.000
0.178
0.002
0.021
9.619
0.042
5.246
0.891
0.001
16.000
0.087
0.008
0.008
9.144
0.022
5.092
1.638
0.002
16.000
0.117
0.000
0.004
9.305
0.020
5.231
1.323
0.000
16.000
0.038
0.002
0.009
9.234
0.031
5.203
1.483
0.001
16.000
0.084
0.002
0.005
9.228
0.020
5.194
1.467
0.000
16.000
0.086
0.004
0.005
9.250
0.030
5.194
1.426
0.004
16.000
0.128
0.006
0.000
9.271
0.028
5.149
1.416
0.001
16.000
109
Table 4
Representative compositions of forsterite in wt.%, Kerimasi jacupirangite, Tanzania.
SiO2
FeOT
MnO
MgO
CaO
Total
42.30
3.00
0.24
54.43
0.01
99.97
39.65
8.80
3.36
47.57
0.53
99.91
39.30
8.75
3.86
47.31
0.61
99.82
39.15
10.12
3.77
46.24
0.62
99.90
40.52
4.95
3.49
50.77
0.20
99.93
39.67
8.00
3.49
48.50
0.20
99.86
40.93
7.68
3.41
47.75
0.16
99.94
40.43
7.54
3.29
48.54
0.12
99.93
39.34
9.98
3.20
46.94
0.44
99.91
40.82
9.02
3.62
45.38
0.44
99.28
Average
n = 15
1SD
Min
Max
40.13
8.21
3.25
47.91
0.37
0.87
2.11
0.85
2.37
0.19
38.92
3.00
0.24
44.56
0.01
42.30
11.95
4.02
54.43
0.63
Min
0.87
Max
0.97

Si
Fe2+
Mn
Mg
Ca
Cation sum
1.006
0.060
0.005
1.930
0.000
3.000
0.980
0.182
0.070
1.753
0.014
3.000
0.974
0.181
0.081
1.748
0.016
3.000
0.975
0.211
0.079
1.718
0.017
3.000
0.984
0.101
0.072
1.838
0.005
3.000
0.977
0.165
0.073
1.780
0.005
3.000
1.010
0.159
0.071
1.756
0.004
3.000
0.994
0.155
0.069
1.779
0.003
3.000
0.977
0.207
0.067
1.737
0.012
3.000
1.024
0.189
0.077
1.698
0.012
3.000
mg#
0.97
0.91
0.91
0.89
0.95
0.92
0.92
0.92
0.89
0.90
End-members (mol.%)
Fo
Fa
Teph
Lar
96.76
2.99
0.24
0.01
86.81
9.01
3.48
0.70
86.26
8.95
4.00
0.80
84.84
10.42
3.93
0.82
91.19
4.99
3.56
0.26
88.00
8.14
3.60
0.26
88.24
7.96
3.58
0.21
88.68
7.73
3.42
0.16
85.85
10.24
3.33
0.58
85.93
9.58
3.89
0.60
Average
n = 15
1SD
Min
Max
87.67
8.46
3.38
0.49
3.18
2.24
0.90
0.25
82.71
2.99
0.24
0.01
96.76
12.45
4.24
0.83
FeOT all Fe expressed as FeO, 1SD one absolute standard deviation, mg# = Mg/(Mg + Fe2+). Foforsterite, Fafayalite, Tephtephroite, Larlarnite.
explained by partitioning of F into the carbonate melt during liquidimmiscibility between silicate and carbonate melts (Guzmics et al.,
2012; Jones et al., 1995; Kjarsgaard, 1998; Mitchell, 2009; Veksler
et al., 2012). In accordance with this hypothesis, uorine-rich phlogopites have also been described from other carbonatite rocks (e.g. Brod
et al., 2001; Seifert et al., 2000).
The major minerals of afrikandite [clinopyroxene (~ 4555 vol.%),

nepheline (~ 2030 vol.%), magnetite (~ 1015 vol.%), perovskite
(~ 1520 vol.%) and melilite (~ 510 vol.%)] are also present in
jacupirangite, although clinopyroxene (~ 6070 vol.%) and magnetite
(~2030 vol.%) are the main rock-forming minerals. Nepheline, perovskite (Fig. 3F) and melilite (Fig. 4A) are also present but only as crystal
Table 5
Representative compositions of phlogopite in wt.%, Kerimasi jacupirangite, Tanzania.
SiO2
TiO2
Al2O3
FeOT
MnO
MgO
CaO
BaO
Na2O
K2O
F
Cl
Total
O = (F,Cl)2
Total
41.02
0.40
14.10
4.03
0.16
24.04
0.05
0.39
0.41
10.25
1.24
0.00
96.11
0.52
95.58
41.22
0.49
14.00
4.04
0.21
23.51
0.09
0.40
0.39
9.88
0.94
0.00
95.16
0.40
94.76
41.69
0.42
14.37
4.06
0.23
23.86
0.11
0.32
0.54
9.49
0.62
0.01
95.72
0.26
95.46
41.16
0.48
13.65
4.21
0.22
23.97
0.08
0.26
0.42
10.01
1.36
0.01
95.82
0.57
95.24
39.70
0.42
14.36
3.77
0.23
25.00
0.03
0.32
0.47
10.46
1.23
0.01
96.00
0.52
95.48
40.79
0.32
14.23
3.49
0.23
24.55
0.04
0.34
0.25
10.56
2.27
0.00
97.07
0.96
96.11
38.72
0.30
14.24
3.85
0.29
23.35
0.06
0.79
0.27
9.82
1.76
0.01
93.45
0.74
92.71
38.75
0.41
14.05
4.74
0.30
23.62
0.06
0.82
0.31
9.70
1.72
0.01
94.47
0.73
93.74
40.21
0.34
13.78
3.88
0.24
24.24
0.12
0.35
0.29
9.94
1.50
0.01
94.89
0.63
94.26
38.30
0.48
14.40
3.54
0.17
23.56
0.09
0.83
0.23
9.85
1.79
0.00
93.24
0.75
92.48
Average
n = 27
1SD
Min
Max
39.59
0.34
13.92
3.89
0.24
23.95
0.11
0.43
0.38
9.89
1.34
0.01
1.37
0.14
0.48
0.41
0.05
0.76
0.09
0.17
0.11
0.48
0.41
0.00
36.96
0.03
12.56
3.24
0.17
22.41
0.01
0.28
0.23
9.41
0.98
0.00
40.79
0.48
14.61
4.74
0.40
25.93
0.32
0.83
0.47
10.79
2.27
0.02

Si
Al(IV)
Al(VI)
Ti
FeT
Mn
Mg
Ca
Ba
Na
K
F
Cl
OH
Cation sum
2.943
1.077
0.116
0.022
0.242
0.010
2.571
0.004
0.011
0.056
0.938
0.281
0.000
1.729
10.000
2.983
1.055
0.139
0.026
0.244
0.013
2.536
0.007
0.011
0.054
0.912
0.214
0.000
1.804
10.000
2.983
1.060
0.151
0.023
0.243
0.014
2.545
0.008
0.009
0.075
0.866
0.140
0.001
1.881
10.000
FeOT all Fe expressed as FeO, 1SD one absolute standard deviation.
2.967
1.059
0.101
0.026
0.253
0.013
2.575
0.006
0.007
0.059
0.920
0.309
0.001
1.703
10.000
2.838
1.148
0.062
0.023
0.226
0.014
2.665
0.003
0.009
0.066
0.954
0.277
0.001
1.715
10.000
2.921
1.091
0.110
0.017
0.209
0.014
2.621
0.003
0.010
0.034
0.965
0.514
0.000
1.491
10.000
2.881
1.130
0.119
0.017
0.240
0.018
2.590
0.005
0.023
0.039
0.932
0.413
0.001
1.592
10.000
2.859
1.145
0.077
0.023
0.292
0.019
2.598
0.004
0.024
0.044
0.913
0.402
0.001
1.600
10.000
2.927
1.090
0.092
0.019
0.236
0.015
2.630
0.009
0.010
0.041
0.923
0.346
0.001
1.662
10.000
2.854
1.155
0.110
0.027
0.221
0.011
2.618
0.007
0.024
0.033
0.936
0.422
0.000
1.582
10.000
110
Table 6
Representative compositions (wt.%) of quenched magnetite-hosted carbonate melt inclusions after heating to 950 C, Kerimasi jacupirangite, Tanzania.
Sample
10
Average
n = 103
1SD
Min
Max
SiO2
TiO2
Al2O3
FeOT
MnO
MgO
SrO
CaO
BaO
Na2O
K2O
P2O5
F
SO3
Cl
Total
O = (F,Cl)2
Total
0.52
0.11
0.31
2.30
0.59
1.83
0.59
42.08
0.23
9.42
1.94
1.90
0.98
0.03
0.31
63.14
0.48
62.66
0.45
0.20
0.23
3.30
0.94
2.48
0.68
43.63
0.24
6.59
1.87
1.63
0.60
0.00
0.38
63.23
0.34
62.89
0.46
0.06
0.19
1.79
0.27
1.05
0.42
44.94
0.04
7.83
0.98
2.02
0.00
0.39
0.02
60.47
0.00
60.47
0.37
0.06
0.11
1.70
0.18
1.20
0.45
46.01
0.08
6.96
0.84
2.00
0.00
0.28
0.02
60.27
0.00
60.26
0.25
1.41
0.12
2.54
0.61
2.32
0.59
36.87
0.22
14.51
1.87
1.65
0.87
0.03
0.71
64.57
0.53
64.04
0.45
0.15
0.06
2.52
0.61
2.10
0.61
43.10
0.27
8.49
1.83
1.77
1.22
0.02
0.42
63.63
0.61
63.02
0.18
0.07
0.01
1.69
0.35
1.62
0.18
34.08
0.62
19.24
2.23
0.81
0.67
0.03
0.79
62.56
0.46
62.10
0.15
0.07
0.03
1.92
0.38
1.96
0.20
34.38
0.63
18.91
2.19
0.87
0.90
0.02
0.96
63.57
0.60
62.97
0.02
0.20
0.13
2.47
0.25
0.59
0.54
36.56
0.08
15.61
2.18
0.68
0.11
0.34
0.10
59.87
0.07
59.80
0.36
0.13
0.05
2.59
0.48
0.90
0.55
44.00
0.12
7.54
1.26
3.54
0.60
1.37
0.16
63.65
0.29
63.36
0.54
0.25
0.11
1.05
0.48
1.51
0.44
39.18
0.26
12.34
2.39
1.68
0.73
0.39
0.40
0.37
0.28
0.12
0.63
0.23
0.82
0.22
3.98
0.29
3.94
0.78
0.70
0.56
0.50
0.34
0.01
0.02
0.01
0.41
0.09
0.00
0.00
23.10
0.00
4.46
0.84
0.26
0.00
0.00
0.00
1.53
1.41
0.95
3.30
1.44
5.05
1.17
50.31
2.17
29.46
4.94
3.67
3.90
1.89
1.71
Major element composition of all the studied 103 magnetite-hosted carbonate melt inclusions can be followed as an electronic supplement, FeOT all Fe expressed as FeO, 1SD one absolute
standard deviation.
inclusions. The main constituents of calciocarbonatite (calcite, apatite,

olivine and phlogopite) are also found interstitially in jacupirangite in
the clinopyroxene- and magnetite-formed cumulate (Fig. 2B and C).
Considering the minerals present and their compositional evolution
(Figs. 9, 10) it is evident that jacupirangite might represent an intermediate member between afrikandite and calciocarbonatite. However, it
remains uncertain as to whether jacupirangite is formed from a separated carbonate melt such as the calciocarbonatite or is it a derivative of a
silicate melt formed after crystallization of afrikandite.
(Figs. 12, 13). This SiO2-enrichment can be explained by the crystallization of afrikandite at high (10501100 C) temperature in the presence
of an immiscible silicate melt, which is reected in the composition of
the coexisting carbonate melt, containing more components (e.g. Si) derived from the parental melilitenephelinite magma (Guzmics et al.,
2012). In terms of alkalis (Na2O + K2O), carbonate melt inclusions
from calciocarbonatite (up to 37 wt.%) and jacupirangite (up to
35 wt.%) show enrichment in these elements relative to those in
afrikandite (up to 24 wt.%) (Fig. 12). Even though the immiscible carbonate coexisting with silicate melt is alkali-poor and CaO-rich in
Kerimasi system (Fig. 12), we did not detect Na2O + K2O concentrations
less than 710 wt.% in the carbonate melt.
In this respect, experiments show that at high T (N1000 C) the carbonate melt coexisting with a silicate melt, contains at least 1 wt.% SiO2
and 710 wt.% (Na2O + K2O) (Brooker and Kjarsgaard, 2011;
Kjarsgaard, 1998; Lee and Wyllie, 1997, 1998a,b; Mitchell, 2009;
Nielsen et al., 1997; Rass and Plechov, 2000; Seifert and Thomas,
1995; Sokolov et al., 1999). On the basis of melt inclusions (Guzmics
et al., 2008b, 2011, 2012, 2015; Mitchell, 2009; Mitchell and Dawson,
2012) and natrocarbonatite data (Keller and Zaitsev, 2012), in naturally
6.2. Carbonate melt inclusions

Comparing the carbonate melt compositions from the melt inclusions of afrikandite, jacupirangite and calciocarbonatite, it is evident
that overall the carbonate melts have similar compositions (Fig. 12), although the concentrations of some elements vary widely. The carbonate
melts in afrikandite are richer in SiO2 (average 1.4 wt.%, n = 44, 1SD =
0.38) (Guzmics et al., 2012) relative to those in jacupirangite (average
0.6 wt.%, n = 180, 1SD = 0.36) (Tables 6 and 7) and calciocarbonatite
(average 0.6 wt.%, n = 133, 1SD = 0.74) (Guzmics et al., 2011)
Table 7
Representative compositions (wt.%) of quenched clinopyroxene-hosted carbonate melt inclusions after heating to 850 C, Kerimasi jacupirangite, Tanzania.
Sample
10
Average
n = 77
1SD
Min
Max
SiO2
TiO2
Al2O3
FeOT
MnO
MgO
SrO
CaO
BaO
Na2O
K2O
P2O5
F
SO3
Cl
Total
O = (F,Cl)2
Total
0.89
0.02
0.11
0.07
0.16
0.93
0.00
41.00
0.19
13.18
1.53
0.94
0.33
0.30
0.33
59.98
0.21
59.76
1.17
0.02
0.01
0.05
0.04
0.15
0.65
36.29
0.30
16.48
2.38
0.64
0.00
0.74
0.08
58.99
0.02
58.97
0.50
0.04
0.07
0.11
0.05
0.63
0.37
42.32
0.23
10.97
2.19
1.36
1.35
0.68
0.39
61.26
0.66
60.60
0.27
0.00
0.09
0.04
0.03
0.01
0.33
35.07
1.04
21.33
2.17
1.76
0.10
0.81
0.34
63.39
0.12
63.27
0.40
0.00
0.01
0.03
0.07
0.18
0.39
35.24
0.06
18.59
2.07
1.01
0.00
0.94
0.07
59.05
0.02
59.03
1.15
0.05
0.04
0.05
0.18
1.00
0.41
42.17
0.00
12.00
1.60
2.44
0.67
0.41
0.58
62.73
0.41
62.32
0.75
0.02
0.04
0.07
0.04
0.22
0.30
40.21
0.10
13.66
1.68
2.43
0.03
0.52
0.08
60.16
0.03
60.13
0.59
0.11
0.04
0.04
0.08
1.96
0.62
40.68
0.46
11.90
1.93
1.49
1.79
0.95
0.11
62.76
0.78
61.99
0.48
0.01
0.03
0.06
0.02
0.38
0.00
32.06
0.05
22.48
1.82
1.00
0.10
0.54
0.05
59.07
0.05
59.01
0.70
0.00
0.08
0.05
0.05
0.73
0.63
43.23
0.12
9.25
1.91
2.19
0.06
1.44
0.09
60.55
0.05
60.50
0.66
0.02
0.07
0.06
0.08
0.55
0.41
39.18
0.20
14.18
2.29
1.39
0.38
0.74
0.26
0.35
0.03
0.08
0.05
0.06
0.49
0.19
3.46
0.24
3.39
0.76
0.60
0.57
0.32
0.29
0.11
0.00
0.00
0.00
0.00
0.00
0.00
24.80
0.00
6.32
0.00
0.00
0.00
0.00
0.00
1.57
0.11
0.42
0.43
0.25
2.16
0.91
47.26
1.47
25.05
4.87
3.16
3.01
1.67
1.64
Major element composition of all the studied 77 clinopyroxene-hosted carbonate melt inclusions can be followed as an electronic supplement, FeOT all Fe expressed as FeO, 1SD one absolute standard deviation.
Carbonate melt (n=180)

35
Na 2O wt. %
30
25
20
15
111
than in the jacupirangite (Fig. 4), suggesting an increase of abundance

of this component as the carbonate melt evolved to lower temperatures.
Overall the compositions of carbonate melt inclusions in jacupirangite
and calciocarbonatite are very similar, but quite different from those in
afrikandite-hosted carbonate melts, and is most apparent in the Si and P
versus alkali and volatile abundances (Fig. 13). Magnetite-hosted carbonate melt inclusions in jacupirangite probably contained a carbonate melt
that separated during afrikandite formation (Figs. 8, 12).
10
5
6.3. Entrapping and crystallization conditions
Magnetitehosted carbonate melt (n=103)

Clinopyroxenehosted carbonate melt (n=77)
0
20
25
30
35
40
45
50
CaO wt. %
Carbonate melt (n=180)
P2O5 /Na2O wt. %
0,1
Magnetitehosted carbonate melt (n=103)

Clinopyroxenehosted carbonate melt (n=77)
0,01
0
10
12
CaO/Na O wt. %
2
Fig. 8. Compositional variation of quenched magnetite- and clinopyroxene-hosted

carbonatite melt inclusions. (A) Na2O versus CaO diagram (wt.%) showing calcite fractionation and (B) P2O5/Na2O versus CaO/Na2O diagram (wt.%) suggesting apatite fractionation.
Gray arrows indicate direction of melt evolution.
occurring carbonate melts, phosphorous is also an essential component.

Considerably higher amounts of P2O5 (average 4.5 wt.%, n = 44, SD =
0.73) are found in carbonate melts in the afrikandite relative to those in
jacupirangite (average 1.5 wt.%, n = 180, SD = 0.65) and calciocarbonatite
(average 1.9 wt.%, n = 103, SD = 0.94) (Fig. 13). This reects the observation that the higher the temperature and the concentration of CaO in the
carbonate melt, the higher the solubility of apatite (Baker and Wyllie,
1992). Thus, decreasing P2O5/Na2O versus CaO/Na2O ratios in carbonate
melt inclusions in jacupirangite indicate apatite and calcite fractionation
(Fig. 8). As P2O5 also partitions into the carbonate melt phase during silicatecarbonate liquid immiscibility (Guzmics et al., 2012, 2015;
Kjarsgaard, 1998; Martin et al., 2012, 2013; Mitchell, 2009), the separated
carbonate melt will crystallize apatite in rock-forming amounts.
Volatiles, such as Cl, F and SO3, in the melt can signicantly inuence
melt viscosity and diffusion during magmatic processes (Mangler et al.,
2014). These components partition into the carbonate melt phase during silicatecarbonate liquid immiscibility (Guzmics et al., 2012, 2015;
Mangler et al., 2014; Veksler et al., 2012). This is reected in the carbonate melt inclusions in jacupirangite (averages Cl = 0.3 wt.%, F =
0.5 wt.%, SO3 = 0.6 wt.%), and calciocarbonatite (averages Cl =
0.4 wt.%, F = 1.0 wt.%, SO3 = 0.7 wt.%), which are enriched in these
components relative to those in afrikandite (Cl b 0.05 wt.%, averages
F = 0.5 wt.%, SO3 = 0.3 wt.%) (Fig. 13).
Nahcolite occurs in the melt inclusions (Fig. 4). It has been shown by
Fall et al. (2007) that nahcolite dissociates to CO2 and water at temperatures of less than 200 C i.e.: 2NaHCO3 = Na2O + H2O + 2CO2. Thus,
the uid phase coexisting with carbonate melt phase at high-T is probably
a low density CO2-dominated uid, undoubtedly containing small
amount of water. Consequently, homogenized carbonate melt also has
to contain small amounts of H2O, in addition to the volatiles mentioned
above. Nahcolite has more commonly been detected in apatite-hosted
carbonate melt inclusions in calciocarbonatite (Guzmics et al., 2011)
The jacupirangite formed in a plutonic environment and the carbonate melt inclusions are now totally crystallized at ambient temperature
and lack a uid bubble (Fig. 3C and D). However, uid bubbles appear
upon heating the inclusions (Fig. 5A). The homogenization temperature
of clinopyroxene-hosted melt inclusions was observed to be between
8501100 C (Fig. 5). High temperatures in this range (e.g. above
900 C) do not necessarily represent the entrapping temperatures (e.g.
Bodnar and Student, 2006; Danyushevsky et al., 2002; Roedder, 1979,
1984) for several reasons. For example, during heating a bubble phase
appears in the inclusions enclosing accidentally trapped calcite crystals
together with small quantities of carbonate melt, similarly to inclusions
containing only carbonate melt. Inclusions with accidentally trapped
calcite could also be homogenized, but at much higher temperature
(e.g. N1000 C) than those of the actual entrapment temperature. Due
to possible heterogeneous trapping of minerals and the potential increase of melt inclusion volumes during heating (Danyushevsky et al.,
2002; Frezzotti, 2001 and Roedder, 1984, 1987), the minimum homogenization temperature is the closest to that, at which the carbonate melt
inclusions were trapped in the fractures of clinopyroxenes. For this purpose we used 850 C (minimum homogenization temperature) for the
heating and quenching experiments of clinopyroxene-hosted carbonate
melt inclusions.
As magnetite is an opaque mineral, the homogenization temperatures of magnetite-hosted carbonate melt inclusions could not be observed. Therefore, we choose 950 C for heating and quenching
experiments of the magnetite-hosted primary carbonate melt inclusions considering that: (1) magnetites coexist with clinopyroxenes
and hence were probably formed at higher temperatures than
clinopyroxene-hosted secondary carbonate melt inclusions (850 C);
and (2) magnetites in jacupirangite most probably crystallized at
lower temperatures than those in afrikandite (10501100 C).
For the estimation of temperature and pressure conditions of crystallization of the interstitial phase assemblage of jacupirangite (calciteapatiteforsteritephlogopite, Figs. 2, 11A), we considered that forsterite and
calcite co-precipitated (Figs. 2, 11A). On the basis of the experimental
work of Franz and Wyllie (1966), in the system CaOMgOSiO2H2O
CO2 co-crystallization of calcite and forsterite from carbonate melt takes
place at temperatures higher than 895 C at 1 kbar (Fig. 11A). By reducing
the temperature from 1000 C to 895 C calcite and forsterite can coprecipitated, whereas at the R7 invariant point (T = 895 C) calcite
can be in equilibrium with both forsterite and monticellite (Fig. 11B).
With further decrease in temperature (T b R7), the crystallization of
forsterite is replaced by monticellite (Fig. 11C).
The forsterite cores of monticellite in Kerimasi calciocarbonatite
(Fig. 11B) (Guzmics et al., 2011) and the coexistence of forsterite and
calcite with the absence of monticellite in Kerimasi jacupirangite
(Figs. 2B and C, 11A) suggest that: (1) the interstitial phase assemblage
of jacupirangite was formed at temperatures higher than 895 C;
(2) calciocarbonatite started to crystallize at temperatures lower than
895 C. The latter conclusion is supported by the minimum homogenization temperature (880 C) of apatite-hosted carbonate-melt inclusions in Kerimasi calciocarbonatite (Guzmics et al., 2011). It is
important to note that carbonate melts with high CaO (~3040 wt.%)
contents similar to those, which produced the jacupirangite magnetites
(Fig. 8), cannot be stable at pressure lower than 12 kbar due to dissociation
112
Kerimasi clinopyroxenes
20
Afrikandite (brown core) (n=10)

Afrikandite (green rim) (n=18)
Guzmics et al. (2012)
Afrikandite (in melt inclusions)
FeO wt. %
15
Jacupirangite (n=67)
Afrikandite
Uncompahgrite
Church (1995)
Ijolite
10
4.3
11
2.8
0.67
Al O wt. %
2 3
2.5
1.5
TiO wt. %
1
0.5
0
Al O wt. %
2 3
MgO wt. %
20
15
10
5
47
48
49
50
51
52
53
54
55
56
SiO wt. %
2
Fig. 9. Compositional evolution of clinopyroxenes in Kerimasi from afrikandite (brown core through green rim) (Guzmics et al., 2012) to jacupirangite (this study). Clinopyroxene compositions studied by Church (1995) are also plotted. Gray arrows indicate compositional change of clinopyroxenes with melt evolution. Italic numbers on the FeOTAl2O3 diagram show the
(Fe + Al)Tschermak's content of the clinopyroxenes in mol.%. Decrease of clinopyroxene in Tschermak's, Al2O3 and TiO2 content can be resulted from the co-precipitation of melilite,
nepheline, perovskite and magnetite. FeOT all Fe as FeO. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
of the carbonate phases into oxides and CO2 (Franz and Wyllie, 1966;
Mitchell, 1986). This could result in the elimination of the carbonate melt
phase. Hence, crystallization temperatures of magnetite-hosted primary carbonate melt inclusions in jacupirangite were higher than 895 C, but lower
than the formation temperature of afrikandite (10001050 C) at minimum
12 kbar pressure.
6.4. What melt were the host phases crystallized from?

On the basis of petrological observations, it is evident that randomly
distributed primary carbonate melt inclusions occur in magnetite
(Fig. 3A), and indicate the presence of a carbonate melt during the formation of magnetite. In contrast, clinopyroxene-hosted secondary carbonate melt inclusions (Fig. 3B) are trapped when clinopyroxenes
have already crystallized, hence the clinopyroxenes did not precipitate
from carbonate melt. In accord with studies by Andreeva (2014) and
Kjarsgaard (1998), we believe that a carbonate melt, containing only
0.6 wt.% SiO2 (Tables 6 and 7), probably will not crystallize
clinopyroxene in rock-forming quantities (Fig. 2A), but rather small
amounts of Si-poor minerals such as forsterite and phlogopite
(Fig. 2B). Clinopyroxene probably crystallized earlier from an alkali
rich, but Al2O3- and TiO2-depleted (peralkaline) silicate melt, coexisting
with an immiscible carbonate melt remaining after afrikandite formation. This is supported by the compositional correspondence between
clinopyroxene coexisting with immiscible silicatecarbonate melts in
perovskite-hosted melt inclusions in afrikandite and clinopyroxenes in
jacupirangite (Fig. 9). We can conclude that clinopyroxene in
jacupirangite might have been formed after afrikandite crystallization
in the presence of immiscible silicate and carbonate melts.
6.5. Origin of carbonate melt entrapped in magnetite and clinopyroxene

Both magnetite- and clinopyroxene-hosted carbonate melt inclusions
are rich in CaO (average 39 wt.%) i.e., they have a relatively unevolved
113
Kerimasi magnetites
12
Afrikandite (n=20) Guzmics et al. (2012)

Calciocarbonatite (n=43) Guzmics et al. (2011)
10
Calciocarbonatite, calcite carbonatitic tuff and lapilli

Reguir et al. 2008
TiO wt. %
0
72
74
76
78
80
82
84
86
88
90
FeO wt. %
12
TiO wt. %
10
10
12
14
MgO wt. %
Fig. 10. Compositional variation of magnetites in Kerimasi jacupirangite (this study), afrikandite (Guzmics et al., 2012) and calciocarbonatite (Guzmics et al., 2011). Compositions of magnetites from Kerimasi occurred in carbonatite tuff and lapilli studied by Reguir et al. (2008) are also plotted to support the separation of TiO2-rich and TiO2-poor magnetites. Gray arrows
indicate the compositional change of magnetites with melt evolution. FeOT all Fe as FeO.
composition compared to effusive natrocarbonatites from Oldoinyo

Lengai (Dawson et al., 1990, 1994; Keller and Zaitsev, 2012) and formed
at higher temperatures (9001000 C), unlike natrocarbonatite lavas,
which have maximum eruption temperatures of 490545 C (Keller and
Krafft, 1990; Krafft and Keller, 1989). Carbonate melts with such CaOrich compositions must be the result of signicant fractionation and/or
immiscibility as experimental (Dalton and Presnall, 1998; Lee and
Wyllie, 1998a,b, 2000; Lee et al., 2000; Ryabchikov and Hamilton, 1993;
Sweeney, 1994; Wallace and Green, 1988) and melt inclusion (Guzmics
et al., 2008a,b) studies have indicated that carbonate melts, which are directly derived from the mantle have a dolomitic composition. The CaOrich nature of the carbonate melt can be a result of strong partitioning
of Ca into the immiscible carbonate melt relative to the other divalent cations (Mg, Fe and Mn) (Guzmics et al., 2012, 2015), and CaO-rich (12
17 wt.%) character of the initial silicate parent e.g. melilitenephelinite
(Guzmics et al., 2012; Kjarsgaard, 1998). Thus, the carbonate melt
entrapped in magnetite and clinopyroxene is rather the product of a silicatecarbonate liquid immiscibility that occurred during formation of
afrikandite (Guzmics et al., 2012) than directly derived from the mantle
by partial melting.
calciocarbonatite (Fig. 8). This negative correlation is indicative of calcite and apatite fractionation, and is consistent with the observation
that calciocarbonatite is present at Kerimasi (Guzmics et al., 2011). Calcite and apatite also appear in the jacupirangite as an interstitial mineral. At lower temperatures (b~ 650 C), CaNaK carbonates (e.g.,
nyerereite, shortite) begin to crystallize from the trapped alkalisaturated carbonate melts (Figs. 3, 4). During further fractionation of
the carbonate melt, in addition to the increase of alkalis, the content of
volatiles such as Cl, F, SO3, CO2 and H2O might also rise considerably,
leading to the formation of water-soluble minerals. These alkali-rich
minerals are present only as daughter phases in the melt inclusions,
and not as mineral phases in the bulk rock.
Identication of minerals such as nyerereite, shortite, nahcolite and
sulfohalite, in carbonate melt inclusions is important as they sequester
the majority of the volatile components of the carbonatite system. Because of the rapid alteration of these minerals in sub-aerial environments
(Kogarko et al., 1991; Zaitsev and Keller, 2006), these volatile-rich minerals are removed and thus their concentrations are negligible in bulk
rock compositions leading to misleading data interpretation and incorrect
conclusions regarding magma origins and carbonatite petrogenesis.
6.6. Importance of study of melt inclusions in carbonatite systems
6.7. Petrogenetic model for formation of jacupirangite and Kerimasi plutonic

rocks
A negative correlation of (Na2O + K2O) versus CaO can be observed

for magnetite- and clinopyroxene-hosted carbonate melt inclusions in
jacupirangite and is similar to that found for inclusions in
A petrogenetic model of Kerimasi plutonic rocks is presented in

Fig. 14. This model shows the general tendency of melt evolution and
114
Mgt
Ap
Cc
Cpx
Cpx
Fo
100 m
Jacupirangite T > R7
B
10 m
Calciocarbonatite
T = R7 (895 C)
Ap
Mo
Ap
Ap
1966
Mo
Cc
Mo Mgt
100m
CO2 (mol. %)
Calciocarbonatite T < R7
Fig. 11. CaOMgOSiO2H2OCO2 system at 1 kbar. This phase diagram shows that co-crystallization of calcite and forsterite with the presence of carbonate melt takes place at temperatures higher than 895 C at 1 kbar. (A) At higher temperature than 895 C calcite and forsterite can co-precipitated, such as in jacupirangite.. (B) At R7 invariant point (895 C) calcite
breakdown (decarbonation) reaction (red line) intersects the liquidus (black line), calcite can be in equilibrium with both forsterite and monticellite as in calciocarbonatite (Guzmics et al.,
2011). (C) On further cooling, crystallization of forsterite is replaced by monticellite as in calciocarbonatite (Guzmics et al., 2011). Back-scattered electron images. Cpx: clinopyroxene; Mgt:
magnetite; Cc: calcite; Fo: forsterite; Mo: monticellite; Ap: apatite; P: periclase; L: liquid; V: vapor.
After Franz and Wyllie, 1966.
not the evolution of a particular melt(s), and is based on all available

melt inclusion data from Kerimasi (this study and Guzmics et al.,
2011, 2012, 2015) together with phase diagrams determined by Lee
and Wyllie (1998a) at 1 GPa. The parental magma is considered to be
a CaO and MgO-rich and CO2-bearing melilitenephelinite initially
held at a temperature of ~1100 C.
Step A: At the early stages of magma evolution clinopyroxene
(brown cores of the clinopyroxenes in afrikandite), nepheline, melilite
and perovskite i.e., Kerimasi afrikandite begin to crystallize. Coprecipitation of clinopyroxene, nepheline and melilite leads to the
melt becoming depleted in Al2O3 and SiO2 and enriched in CaO.
Step B: The changes in melt composition, during afrikandite crystallization, result in immiscibility and formation of separate silicate, carbonate and sulde melts (~ 1050 C). The precipitation of perovskite
leads to depletion in the TiO2 content of the melts. During further fractionation, there is a decrease in the Tschermak's component of
clinopyroxene and green diopsidic clinopyroxene begins to crystallize
from the TiO2- and Al2O3-depleted silicate melt (~ 10001050 C).
Green clinopyroxene appears on the rims of brown-cored
clinopyroxenes of the afrikandite.
Step C: The immiscible silicate and carbonate melt physically separate
from sulde melt and from the afrikandite body and the silicate melt crystallizes further green diopsidic clinopyroxene giving the bulk of the
jacupirangite. Precipitation of melilite and nepheline continues and
minor amounts are entrapped in green clinopyroxene.
Step D: The immiscible carbonate melt separates from the silicate fraction however, some carbonate melt remains interstitially in the
clinopyroxene aggregates. At ~9501000 C magnetite begins to crystallize from the carbonate melt fractions those have already been physically
separated and are also present interstitially. At this time primary carbonate melt inclusions are enclosed in the magnetite.
Step E: Magnetite crystals, precipitated from the separated carbonate melt at STEP D, sink into clinopyroxene-rich crystal-liquid mush.
The crystallization of calcite, apatite, perovskite, forsterite and phlogopite begins from the interstitial carbonate melt at ~950 C. The composition of this carbonate melt corresponds with the initial melt
composition of calciocarbonatite. For some unknown (mechanical) reason clinopyroxenes are fractured and secondary carbonate melt inclusions are emplaced along the fractures. From the interstitial carbonate
melt, magnetite, apatite, calcite, phlogopite and forsterite crystallize
(N895 C) forming the interstitial phase assemblage of the
jacupirangite. The residual melt becomes more enriched in alkalis.
Step F: Kerimasi jacupirangite crystallizes. Cracks and cleavages of
clinopyroxenes are healed, creating the secondary planes of carbonate
melt inclusions.
Kerimasi calciocarbonatite starts to crystallize at ~ 880900 C
from the carbonate melt fraction that was physically separated at
Step D. Fractionation of this carbonate melt leads to an alkali enrichment similar to the composition of natrocarbonatites (Guzmics et al.,
2011).
It should be noted that this model is not complete either in the very
early or the late evolutional stages of silicate melt. As suggested by
Church (1995) and Guzmics et al. (2012), it is probable that olivine fractionation occurred before formation of afrikandite. Enrichment of
clinopyroxenes in aegirine components from Kerimasi ijolites (Church,
1995; Figs. 7 and 9 in this study) indicates a further evolution of silicate
melt that remained after formation of jacupirangite. Additional study of
melt inclusions in early formed olivine-rich rock and in ijolitic rocks are
required to clarify the melt evolution pathway (Figs. 12 and 14) at
Kerimasi. Considering the evolutionary stages of a silicatecarbonate
melt system, jacupirangites probably began to form when an immiscible
silicatecarbonate melt exists, however, by the end of crystallization
only the presence of the carbonate melt can be recognized.
Jacupirangites are found in many alkaline massifs (Bergstl, 1972;
Brooks et al., 1981; Butakova, 1961; Campbell, 1961; Dawson, 2008;
Dawson and Smith, 1992; Derby, 1891; Erickson and Blade, 1963;
Na2O+K2O
EMPA-determined compositions of
melt inclusions Guzmics et al., 2012
(Kerimasi afrikandite, Tanzania):
115
EMPA-determined compositions of
carbonate melt inclusions
(Kerimasi jacupirangite, Tanzania)
90
90
perovskite-hosted Mg- and Si-rich silicate melt
magnetite-hosted carbonate melt inclusions

(primary)
nepheline-hosted Mg- and Si-rich silicate melt
clinopyroxene-hosted carbonate melt inclusions

(secondary)
perovskite-hosted silicate melt

OLDOINYO LENGAI
CARBONATE MELTS
nepheline-hosted silicate melt
Estimated miscibility gap

(Guzmics et al., 2012)
magnetite-hosted silicate melt
*
*
coexisting immiscible silicate

and carbonate melts in perovskite
perovskite-hosted carbonate melt
weight %
50
50
*
**
*
700
OLDOINYO LENGAI
SILICATE MELTS
750
850
KERIMASI
CARBONATE MELTS
**** ** **
*
105
10
10
1
KERIMASI
SILICATE MELTS
SiO2+TiO2 10
+Al2O3+P2O5
50
90 CaO+MgO
+FeOT+MnO
Magnetite-hosted carbonate melt inclusions, Kerimasi calciocarbonatite, Guzmics et al., 2011, EMPA
Apatite-hosted carbonate melt inclusions, Kerimasi calciocarbonatite, Guzmics et al., 2011, EMPA
(Oldoinyo Lengai) and experimentally determined immiscible carbonate and silicate melts,
* Natural
Kjarsgaard et al., 1995
Immiscible carbonate and silicate melts in nepheline-hosted melt inclusions, Oldoinyo Lengai,
Mitchell, 2009
Melilite-hosted silicate melt inclusions, Gardiner complex, Nielsen et al., 1997
Melilite- and perovskite-hosted carbonate melt inclusions, Gardiner complex, Nielsen et al., 1997
Melilite- and monticellite-hosted carbonate melt inclusions, Krestovskiy massif, Panina, 2005
Olivine-hosted silicate melt inclusions, Elbe zone, Seifert and Thomas, 1995
Olivine-hosted silicate melt inclusions, Guli massif, Rass and Plechov, 2000
Experimentally produced immiscible carbonate and silicate melts,
(Kjarsgaard,1998; 1000oC, 0.5 GPa)
Fig. 12. Hamilton projection (Hamilton et al., 1979) of the quenched carbonate melt inclusions hosted in clinopyroxene and magnetite in Kerimasi jacupirangite. For comparison, the composition of natural immiscible carbonate and silicate melt inclusions together with experimental data is also plotted. Tie-lines connect the conjugate silicatecarbonate compositions studied by Guzmics et al. (2012), Kjarsgaard et al. (1995), and Mitchell (2009). Numbers on the lines indicate temperatures (in C) determined by Guzmics et al. (2012) and Kjarsgaard et al.
(1995). Melt inclusion data reveal that the carbonate melt became enriched in alkalis and depleted in divalent cations, SiO2 and P2O5 after physical separation from the immiscible silicate
parent melt with decreasing temperature.
Kerimasi carbonate melts

12
Afrikandite (n=44)
Calciocarbonatite (n=133)
SiO2+P2O5 wt. %
10
Jamieson and Talkington, 1980; Robins, 1972; Treiman and Essene,

1984; Vuorinen and Hlenius, 2005; Washington, 1901; Yang and
Woolley, 2006), suggesting that silicatecarbonate liquid immiscibility
could take place in all of these complexes.
7. Conclusions
This investigation shows how important it is to study melt inclusions

in alkaline and carbonatite rocks as these rocks rapidly alter due to
weathering processes. Studying only bulk rock compositions leads to incorrect interpretations of their petrogenesis. In this study we highlight
the importance of high-temperature heating experiments and the role
of Raman spectrometry in identifying carbonate melt inclusions and
their daughter phases, especially those, which are water-soluble (e.g.,
nyerereite, nahcolite, sulfohalite). To understand the melt evolution of
jacupirangite, its formation is considered on the basis of the previously
investigated Kerimasi afrikandite and calciocarbonatite, as they are genetically closely-linked.
The composition of the trapped carbonate melt inclusions, in magnetite and clinopyroxene, is very similar (CaO-rich and alkali-bearing)
to the parental melt of Kerimasi calciocarbonatite. Considering the
4
2
0
0
10
15
20
25
30
35
Na2O+K2O+SO3+Cl+F wt. %
Fig. 13. Compositional variation of quenched carbonate melts in Kerimasi jacupirangite
(this study) afrikandite (Guzmics et al., 2012) and calciocarbonatite (Guzmics et al,
2011). The gure shows that the carbonate melts at Kerimasi became enriched in volatiles
and depleted in P2O5 and SiO2 with melt evolution (from stage afrikandite to
calciocarbonatite through jacupirangite).
116
homogenization temperatures of clinopyroxene-hosted carbonate melt

inclusions and mineral stability relations (forsteritemonticellite), the
crystallization temperatures are estimated to be in the range of 900
1000 C at the early stage of magma evolution, i.e., lower than formation
temperature of afrikandite but higher than that of calciocarbonatite. On
the basis of these differences in crystallization conditions and the compositional data for clinopyroxenes and magnetites from Kerimasi plutonic rocks, jacupirangite represents an intermediate stage between
afrikandite and calciocarbonatite stage in the evolution of the Kerimasi
magmas.
Our data show that immiscible silicate and carbonate melt most
probably were present at an early stage during jacupirangite formation,
however, at a later stage we have found evidence for the existence only
of a carbonate melt. The early-formed nature of the jacupirangite is also
supported by unevolved compositions of the clinopyroxenes. Thus
jacupirangite represents a crucial stage in Kerimasi magma development. We have proposed a petrogenetic model for the genesis of
jacupirangite including other Kerimasi plutonic rocks, which could be
a model for reconstructing magma evolution in other alkaline
carbonatite complexes where jacupirangite occurrences have been reported. Overall, the composition of the carbonate melt is characterized
by enrichment of volatiles (Na2O + K2O + F + Cl + S + H2O) from
high (stage afrikandite) to lower temperatures (stages jacupirangite
and calciocarbonatite).
Acknowledgments
This research was granted by the Hungarian Science Foundation
(OTKA PD 105364 to T. Guzmics). Part of these results has been carried
out in the framework of the REG_KM_INFRA_09 Gbor Baross Programme and TMOP project nr. 4.2.1/B-10-2011-0002 by the
European Union and the European Social Fund. R. H. Mitchell's work
on alkaline rocks is supported by the Natural Sciences and Engineering
Research Council of Canada. The authors owe thanks to Zsolt Bend at
Etvs University for his technical help in BSE imaging. The authors
would also like to thank to Professor Andrew Kerr for his editorial
work and to the anonymous reviewers for their constructive comments
and suggestions. This is No 80 publications of Lithosphere Fluid Research Lab at Etvs University, Budapest. This work is dedicated to
the memory of John Barry Dawson.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.lithos.2015.09.011.
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Lithos 238 (2015) 101119

Contents lists available at ScienceDirect

A melt evolution model for Kerimasi volcano, Tanzania: Evidence from

R. Kldos et al. / Lithos 238 (2015) 101119

Pyroclasts of Oldoinyo Lengai

fine-bedded carbonatite tuff

massive bedded carbonatite tuff

carbonatite tuff-pisolithic facies

R. Kldos et al. / Lithos 238 (2015) 101119

For the heating and quenching experiments a furnace technique was

5.1. High resolution Raman microspectrometry

R. Kldos et al. / Lithos 238 (2015) 101119

Fig. 3. Magnetite- and clinopyroxene-hosted carbonate melt inclusions in Kerimasi

[Na2Ca2(CO3)3], calcite (CaCO3), burbankite [(Na,Ca)3(Sr,Ba,Ce)3(CO3)5]

5.3. Compositions of the rock-forming minerals

R. Kldos et al. / Lithos 238 (2015) 101119

Rock-forming mineral phases

Intensity (arbitrary unit)

Intensity (arbitrary unit)

Raman shift (cm )

Raman shift (cm )

Fig. 5. Microthermometric homogenization experiment of clinopyroxene-hosted carbonate

Fig. 6. Characteristic magnetite- (A, B) and clinopyroxene-hosted (C) quenched carbonate

R. Kldos et al. / Lithos 238 (2015) 101119

Formula based on 3 cations and 4 oxygens

5.4. Major element composition of quenched melts

6.1. Jacupirangite mineral compositions comparison with Kerimasi

R. Kldos et al. / Lithos 238 (2015) 101119

Formula based on 4 cations and 6 oxygens

Tschermak's content of co-precipitated clinopyroxene (Carmichael

relationship between afrikandite and jacupirangite. Overall the Kerimasi

R. Kldos et al. / Lithos 238 (2015) 101119

melilite nephelinite (Kerimasi), Church, 1995

ijolite (Kerimasi), Church, 1995

calcite carbonatite (Aley) Reguir et al. 2012

clinopyroxene-apatite-calcite carbonatite (Eden Lake) Reguir et al. 2012

phlogopite-clinopyroxene-calcite carbonatite (Aln) Reguir et al. 2012

andradite-diopside-calcite silicocarbonatite (Oka) Reguir et al. 2012

clinopyroxene-calcite carbonatite (Ozernyi) Reguir et al. 2012

phlogopite-diopside-calcite carbonatite (Turiy Mys) Reguir et al. 2012

vibetoite (Fen complex), Mitchell, 1980

Formula based on 16 cations and 25 anions (O, F, Cl)

1SD one absolute standard deviation.

R. Kldos et al. / Lithos 238 (2015) 101119

Formula based on 3 cations and 4 oxygens

The major minerals of afrikandite [clinopyroxene (~ 4555 vol.%),

Formula based on 10 cations and 11 oxygens

FeOT all Fe expressed as FeO, 1SD one absolute standard deviation.

R. Kldos et al. / Lithos 238 (2015) 101119

inclusions. The main constituents of calciocarbonatite (calcite, apatite,

6.2. Carbonate melt inclusions

R. Kldos et al. / Lithos 238 (2015) 101119

Carbonate melt (n=180)

than in the jacupirangite (Fig. 4), suggesting an increase of abundance

6.3. Entrapping and crystallization conditions

Magnetitehosted carbonate melt (n=103)

Carbonate melt (n=180)

P2O5 /Na2O wt. %

Magnetitehosted carbonate melt (n=103)

Fig. 8. Compositional variation of quenched magnetite- and clinopyroxene-hosted

occurring carbonate melts, phosphorous is also an essential component.

R. Kldos et al. / Lithos 238 (2015) 101119

Afrikandite (brown core) (n=10)

Guzmics et al. (2012)