Economic Geolog

Vol. 78, 1988, pp. 1721-1728

LOW-TEMPERATURE GLASS QUENCHED FROM A SYNTHETIC, RARE EARTH
CARBONATiTE: IMPLICATIONS FOR THE ORIGIN OF THE
MOUNTAIN PASS DEPOSIT, CALIFORNIA
ADRIAN P. JONES AND PETER J. WYLLIE
Division of Geological and Planetart/ Sciences, California Institute of Technologt, Pasadena, California 91125
Introduction
Synthetic carbonatite magmas are represented by
melts in the system CaO-CO2-HaO (Wyllie and Tut-
tle, 1960), and the relation between carbonatites and
silicate magmas has been investigated by addition of
other components (e.g., Wyilie, 1966, 1978). We are
presently determining the phase relations in a series
of systems involving CaO-CaFa-La(OH)s-COa-HaO
and other components in an effort to delineate the
conditions for the precipitation of rare earth carbon-
ates and fiuocarbonates (bastnaesite-type minerals)
from synthetic carbonatite magmas. As a supplement
to the construction of phase diagrams in systems char-
acterized by limited numbers of components, we have
studied a more complex bulk composition which we
believe approximates that of the Sulphide Queen car-
bonatite at Mountain Pass, California--prior to crys-
tallization.
The unusual abundance of bastnaesite (CeFCOs) in
the Sulphide Queen carbonatite body elevates the rare
earths to the status of a major component, compared
with their much lower trace to minor element status
in most other carbonatites. The carbonatite at Mountain
Pass is also unusual for its high barite content and low
silicate and magnetite contents (Olson et al., 1954).
The origin of this body is unknown, but if it is of an
igneous parentage, then the mineralogy suggests low
temperatures and possible residual characteristics re-
suiting from, for examp!e, prolonged or extensive crys-
tal fractionation. Therefore, an experimental study of
this unique carbonatite was undertaken to test the hy-
pothesis that it is of igneous origin and to provide clues
for possible genetic links connecting it with more typ-
ical silicate- and magnetite-bearing carbonatites.
The Sulphide Queen Carbonatite,
Mountain Pass, California
According to Heinrich (1966, p. 178), bastnaesite is
both the most abundant and the most widely distributed
of the dozen or so discrete rare earth carbonate minerals
reported from carbonatites; volumetrically it is typically
of accessory or minor status. However, in the Sulphide
Queen carbonatite at Mountain Pass, California, bast-
naesite forms 5 to 15 percent of the orebody and locally
exceeds 60 percent of the rock. Since its discovery in
1951, this body has been mined commercially as a
major rare earth deposit. In 1980 it was estimated to
contain 40 million tons of ore containing 12 percent
bastnaesite, with an annual production of one-third of
a million tons. The most abundant rock of the body
consists of calcite (40-75%), barite (15-50%), and bast-
naesite (5-15%) (Heinrich, 1966, p. 857). Dolomite is
also a major constituent in parts of the orebody (Olson
et al., 1954). The most abundant carbonatite dikes
associated with the carbonatite body contain calcite
(up to 90%), barite (5-80%), and bastnaesite (locally
up to 80%). The rare earth elements are chiefly of the
cerium subgroup and are very enriched in the lightest
rare earths.
Synthetic Starting Mixture
We selected a composition containing representa-
tives of the main components of the Sulphide Queen
carbonatite, in proportions consistent with its com-
position but with a major consideration being to obtain
a mixture with a low liquidus temperature. The mixture
is estimated to be fairly close to the quaternary eutectic
in the system CaCOs-Ca(OH)a-CaFa-BaSO4, based on
the known phase relationships in the systems CaO-
COa-HaO (Wyllie and Tuttle, 1960), CaCOs-Ca(OH)a-
CaF2 (Gittins and Tuttle, 1964), and CaCOs-Ca(OH)a-
BaSO4 (Kuellmer et al., 1966). Ca(OH)a is required in
the synthetic systems, in the absence of MgO, to bring
down the liquidus temperature. CaFa was added to
provide fluorine for the fluocarbonate, and BaSO4 was
included as barite, which is an essential mineral in this
carbonatite. The rare earth elements were represented
by 20 percent La(OH)$. The mixture selected contained
81.2 percent CaCOs, 24.9 percent Ca(OH)a, 18.5 per-
cent CaF2, 10.4 percent BaSO4, and 20.0 percent
La(OH)$. The composition of the mixture expressed
as a chemical analysis is listed in Table 1.
Experimental Results
The mixture was sealed in gold capsules and run in
cold seal pressure vessels at 1 kbar for 2 to 8 days at
temperature intervals between 700 and 500C. The
subsolidus assemblage consisted of calcite, portlandite,
barite, fluorite, and lanthanum hydroxide. The solidus
temperature was 548 4- 7C. The liquidus was brack-
eted between 625 and 650C. Between the solidus
and liquidus, the quenched assemblages of crystals
0861-0128/88/226/1721-852.50 1721
1722 SCIENTIFIC COMMUNICATIONS
TABLE 1. Electron Probe Analysis of Carbonate Glass
Compared with Starting Mixture
Mixture Glass a
wt percent
Cao s 46.03 45.0
BaO 6.81 6.59
La2Os 4 17.16 18.2
SOs 3.55 3.08
F s 6.58 6.2 s
COo 13.71
H20 8.90
Total - O = F 99.97
Total - (CO2, HaO, O = F) 77.35 76.46
Average of 9 spots, using defocused beam ('10/am), 15 kV,
and 0.4'/aA with routine wavelength dispersive procedures and
LaNi5 as La standard
e Refractive index of glass = 1.588
a Includes CaO equiv. to CaFe, resolved in total
4La as La(OH)a in starting mix
5 Precision for F is much poorer (' __0.5%) than for other ele-
ments
+ liquid consisted of quenched liquid in contact with
various minerals.
Lanthanum hydroxide (La(OH)3) occurs as distinc-
tive elongated prisms, with relatively high birefrin-
gence, and sometimes shows.hexagonal cross sections.
Experiments in the gystem Nd203-H20-CO2 at 1.5 kbar
by Kutty et al. (1978) showed that the Nd equivalent
(Nd(OH)-hexagonal) is stable only under very CO2-
poor conditions, and that under other conditions (i.e.,
Xco > 0.02), the stable phase from 250C to a max-
imum of --580C is Nd(OH)COa-hexagonal, which is
a simple hydroxyl analogue of bastnaesite.
Runs from temperatures well above the liquidus
quenched to a clear glass, with a rind of dendritic
crystallites. Runs from nearer the liquidus quenched
to a clear glass with a similar rind, as illustrated in
Figure 1A and B, with additional scattered spherulitic
clusters, some containing dendritic crystals which form
pale brown aggregates. Glass was detected among the
quench crystals even within the interval of crystals +
liquid.
In all previous experiments with synthetic carbon-
atite magmas, the liquids crystallized completely dur-
ing the quench. No glass has been reported. There-
fore, the preservation of any glass at all was unex-
pected, and the fact that the main mass of the liquid
quenched from 650C was preserved as clear glass
was surprising. No glass has been discovered in our
other experiments with mixtures of the same com-
ponents without BaSO4, and no glass was reported by
Kuellmer et al. (1966) in their study of CaCOa-
Ca(OH)-BaSO4 without La(OH)a. On the basis of
this limited evidence, it appears that some combi-
nation of La, Ba, and possibly (SO4) is required to
yield glass. The reasons should become clearer as we
pursue our study of these complex systems. There was
no sign of the formation of a separate vapor phase,
and the liquid quenched to a clear, bubble-free glass.
FIG. 1. Clear glass charge quenched from synthetic Sulphide Queen carbonatite (see text) viewed in
plain polarized light (A) and in crossed nieols (B). The charge measures approximately 2 mm in width
and has a partly devitrified rind, pale colored in B, as well as eonehoidal fracture. Run 96, temperature
= 650C, pressure = I kbar, duration = 51 hours. See Table I for the composition of the glass as measured
by microprobe.
SCIENTIFIC COMMUNICATIONS 1725
The glass was analyzed by electron microprobe and
is compared in Table 1 with the starting mixture. The
averaged probe analysis total is 76.5 wt percent, with
the balance allotted to unanalyzed H20 and CO2, and
this is consistent with the composition of the starting
mixture, where HO q- CO = 22.6 percent. The re-
fractive index of the glass illustrated in Figure I was
measured at 1.588 _ 0.002.
The glass clearly represents a quenched liquid
which contained a variety of volatile species. Based
on the close agreement between the probe analyses
and the starting mixture, the liquid contained about
33 wt percent of dissolved volatile components,
namely 13.7 percent CO, 8.9 percent HO, 6.6 per-
cent F, and 3.6 percent SOs. This liquid has a com-
position suitable for complete crystallization into the
minerals of the original mixture, without evolution
of gases, as shown by the subsolidus assemblage.
Applications
The results from our synthetic rare earth carbonatite
mixture indicate that the addition of H20 is all that
is required to permit the analogous carbonatite at
Mountain Pass, California, to exist as a liquid magma
at a low pressure and at a temperature near 650C.
These preliminary results do not prove that the Sul-
phide Queen carbonatite was once a liquid magma,
but they confirm that the rock could have been pre-
cipitated from a magma at low temperatures. Liquid
would persist in the magma down to solidus temper-
atures near 543C, or even lower, as a result of the
additional components present in the real system. If
volatile components should be evolved during the clos-
ing stages of crystallization at low pressures, these
would probably be dominated by H20 (Wyllie and
Tuttle, 1960).
The rare earth mineral precipitated from this liq-
uid is not bastnaesite. However, it has been shown by
Kutty et al. (1978) that bastnaesite (as Nd(OH)COs)
is stable in the presence of mixtures of CO q- HO
up to temperatures of about 580C, varying some-
what according to the value of CO/HO in the fluid
phase. At higher temperatures, hydroxyl-bastnaesite
(taking La(OH)COs -- Nd(OH)COs, etc.) is unstable
with respect to La20COs, except for the lowest val-
ues of CO/HO, where La(OH)$ is stable.
This demonstration that a synthetic carbonatite
mixture with the components required for formation
of bastnaesite has a low liquidus temperature, with
liquid persisting through 85C below the inferred
upper stability limit for bastnaesite, is a strong indi-
cation that bastnaesite could be coprecipitated with
calcite from a similar mixture with suitable propor-
tions of COa, H20, and F.
Therefore, we suggest that the evidence from these
experiments is compatible with a magmatic origin for
the Sulphide Queen carbonatite, and that the bast-
naesite in the carbonatite could have been precipi-
tated from such a carbonatite magma. We hope that
our continued experiments in these systems will pro-
vide a clearer picture of the relations between this
unique carbonatite and the more typical carbonatite
parent from which it was presumably derived. The
nature of the parent silicate-carbonate magma from
which the rare earth carbonatite magma was ulti-
mately derived represents a further step in the in-
vestigation.
Acknowledgments
We thank A. N. Mariano for bringing our work to
the attention of R. J. Floran of Union Oil Research,
and R. J. Floran for his encouragement and for in-
formation about the Sulphide Queen carbonatite.
This research was supported by the Earth Sciences
Section of the U.S. National Science Foundation,
grant EAR-8108599.
April 14, Magi 24, 1983
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