Geochimicaet CosmochimicaActa, Vol. 61, No. 22, pp.

4745-4760, 1997
Pergamon Copyright© 1997Elsevier ScienceLtd
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PII S0016-7037(97) 00292-5

Rare earth elements in apatite: Uptake from H20-bearing phosphate-fluoride melts

and the role of volatile components

MICHAEL E. FLEET1 and YUANMINGPAN2

1Department of Earth Sciences, University of Western Ontario, London, Ontario N6A 5B7, Canada
2Department of Geological Sciences, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2, Canada

(Received April 3, 1997; accepted in revised form July 28, 1997)

Abstract- The partitioning of rare earth elements (REEs) between fluorapatite (FAp) and H20- bearing
phosphate-fluoride melts has been studied at about 700 and 800°C and 0.10-0.15 GPa. REE uptake
patterns, i.e., plots of D(REE:FAp/melt), are convex upwards and peak near Nd for single-REE substi-
tuted FAp at minor (0.03-0.25 wt% REE203) abundances, and binary(LREE + HREE)-substituted
FAp, and hexa-REE-substituted FAp at minor to major (0.25-7.8 wt% REE203) abundances. Partition
coefficients for minor abundances of REE and depolymerized phosphate melts are about 5, 8, and 1 for
La, Nd, and Lu, respectively and broadly comparable to those for early fluorapatite in the fractionation
of melts of basaltic composition. The Ca2 site exerts marked control on the selectivity of apatite for
REE because it preferentially incorporates LREE and its effective size varies with substitution of the
A-site volatile anion component (F, C1, OH). Using simple crystal-chemical arguments, melt(or fluid)-
normalized REE patterns are predicted to peak near Nd for fluorapatite and be more LREE-enriched for
chlorapatite. These predictions are consistent with data from natural rocks and laboratory experiments.
The wide variation in D(REE:apatite/melt) in nature (from < 1 for whitlockite-bearing lunar rocks to
about 100 for evolved alkalic rocks) is attributed largely to the influence of the volatile components.
Copyright © 1997 Elsevier Science Ltd

1. INTRODUCTION Green, 1981; Chazot et al., 1996). However, the application

Apatite is an important carrier of rare earth elements (REEs)
in sedimentary, igneous, and metamorphic rocks (e.g., Gro-
met and Silver, 1983; Fleischer and Altschuler, 1986; Soren-
sen and Grossman, 1989; Raimbault et al., 1993; Pan and
Fleet, 1996a; Chazot et al., 1996). Apatite and related Ca
phosphates also host REEs in biomass, soils, and sediments
(Wright et al., 1984; Grandjean-Lrcuyer et al., 1993).
REE substitute for Ca in the two Ca positions of the apatite
structure (Cal: ninefold coordinated, CaO9, tricapped trigonal
prism; Ca2: sevenfold coordinated, CaOrA, A = F, C1, OH,
irregular polyhedron). The multiplicity of Cal is 4 and of
Ca2 is 6, giving an ideal structural formula of Ca14Ca26-
(PO4)rA2. Light and middle REEs (LREEs, MREEs) have
a marked preference for the Ca2 site over the Cal site
(Hughes et al., 1991; Fleet and Pan, 1995a). Apatite com-
monly exhibits only a weak selectivity among REEs, and its
chondrite-normalized REE pattern generally reflects that of
the whole-rock. However, normalization by the appropriate
melt composition reveals slightly convex-upward patterns
that peak at Sm --* Gd for fluorapatite in igneous rocks (e.g.,
Fig. 1 ). The REE patterns for synthetic fluorapatite/melt(or
fluid) are also convex upward and peak at Sm for La, Sm,
Dy, and Lu and melts of basanite to granite composition
(Watson and Green, 1981), at Gd for Ce, Gd, and Yb and
aqueous fluid (Ayers and Watson, 1993), and at Nd for
eleven REEs and H20-bearing phosphate-fluoride melts
(Fleet and Pan, 1995b).
Apatite may significantly affect the distribution of REEs
during partial melting and fractional crystallization of igne-
ous rocks (e.g., Beswick and Carmichael, 1978; Watson and
4745
of experimental partitioning data for REEs to the study of
the fractionation of trace elements in igneous petrogenesis
is complicated by the very wide variation of the ratio of
REEs in apatite to REEs in coexisting melt [D(REE:apatite/
melt)] in nature (e.g., Frey et al., 1980; Watson and Green,
1981 ). The variation in REE ratios between natural fluora-
patite/melt pairs is greater than 2 orders of magnitude (e.g.,
Fig. 1 ). REEs are mildly incompatible with respect to apatite
in lunar rocks, compatible in cumulate rocks and megacrystic
alkali basalts, and highly compatible in evolved acidic and
alkalic igneous rocks. There is also a wide variation in labo-
ratory partition coefficients [D(REE)] for partitioning of
REEs between fluorapatite and silicate melts (Watson and
Green, 1981), for which average D(REE) values varied
from about 3 to 30 and increased systematically with de-
crease in temperature and increase in SiO: content of the
melt.
The dependence of D(REE:clinopyroxene/melt) on SiO2
content is generally attributed to a decrease in the number
of melt sites suitable for REE 3+ cations with increase in the
degree of polymerization (Watson, 1976; Ellison and Hess,
1989; Gaetani and Grove, 1995 ). Jolliff et al. (1993) attrib-
uted the very low values of D(REE:fluorapatite/melt) in
whitlockite-bearing lunar rocks to the relatively higher tem-
peratures expected for lunar magmas and somewhat lower
SiO2 and Na20 contents. They noted that other melt compo-
nents could be contributing factors as well, citing the positive
correlation between REE abundances and C1 content re-
ported by Murrell et al. (1984) for fluorapatite coexisting
with whitlockite.
In a departure from the prior emphasis on melt composi-
4746 M.E. Fleet and Y. Pan

10 3 . . . . . . . . . . . . . . . (Fleet and Pan, 1995a, 1995b; Pan and Fleet, 1996b), con-
cluding that selectivity for REEs is controlled largely by the
Ilimaussaq intrusion effective size of the Ca position(s). In the present paper,
E 102 ~--~ we develop our earlier experimental study on the uptake of
Skaecgaardintrusion Peninsula Ranges batholith REEs by fluorapatite from H20-bearing phosphate-fluoride
melts (Fleet and Pan, 1995b), investigating in greater depth
101
minor (0.03-0.25 wt% REE203 ) contents of REEs in single-
2
O
:3
REE-substituted fluorapatites, and minor to major ( 0 . 2 5 - 7 . 8
¢:
,',i 100 wt% REE203) contents of REEs in b i n a r y [ L R E E + h e a v y
UJ lunar rocks REE ( H R E E ) ] - and hexa-REE-substituted fluorapatites. We
also discuss the influence of volatile components (F, CI,
10 -1 H20) on the form of melt-normalized REE patterns and the
I i I I I I I I I I I I i I I
uptake of REEs by apatite, using crystal-chemical reasoning
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu and analysis of data for natural and synthetic apatite.
Fig. l. Melt-normalized REE patterns for fiuorapatite (FAp) from
lunar rocks (full circles; Jolliff et al., 1993), Skaergaard layered 2. E X P E R I M E N T A L PROCEDURES
series (upper zone, open squares; Paster et al., 1974), granodiorite
from the eastern Peninsular Ranges batholith, southern California Crystals of REE-substituted fluorapatite (FAp) were synthesized
(apatite/whole rock data; open circles; Gromet and Silver, 1983), from HzO-bearing melts using a standard cold-seal hydrothermal
and the Ilfmaussaq intrusion, South Greenland (sodalite foyalte; tri- reaction vessel (Fleet and Pan, 1995b; Table 1 ). The eleven REEs
angles and crosses are ranges in REE content of FAp; R(hnsbo, 1989; investigated were lanthanum, cerium, praseodymium, neodymium,
Larsen, 1979). samarium, europium, gadolinium, dysprosium, erbium, ytterbium,
and lutetium. Cerium was obtained as CeF3, Pr as PrC13" 6H20, and
the remaining REEs as REE203. Starting materials were prepared
from a 1:1 molar mixture of tribasic calcium phosphate [~Cal0-
fion and structure, Gaetani and Grove (1995) investigated (PO4)6 (OH)2 ] and CaF2, combined in the stoichiometric proportions
crystal-chemical controls on the partitioning of REEs be- of fluorapatite [Cat0(PO4)~2] (FAp), and REE203 or REE halide
tween Ca-rich clinopyroxene and basaltic melt, demonstra- (99.99 wt%), CaF2, and SiO2, combined in the stoichiometric pro-
portions of the britholite-like component [Ca4REE6(SiO4)6F2].
ting a sensitive dependence of D ( C e , Y b ) on Ca-Tschermak- These starting materials were appropriately diluted with FAp mixture
ite content of the clinopyroxene. This work provided the to give (Ca,REE) phosphate mixtures with about 0.05-0.06 wt%
basis for a thermodynamic analysis of the partitioning of REEzO3 for experiments on series D and E single-REE-substituted
REEs between clinopyroxene and melt (Blundy et al., FAp and the equivalent of 10 mol% total CaaREE6(SiO4)6F2 for
experiments on binary(LREE+HREE)- and hexa-REE-substituted
1996). FAp. Charges consisted of about 0.040 g (Ca,REE) phosphate mix-
W e have recently investigated crystal-chemical controls ture, 0.040 g of NaF, and 0.01 g of deionized water contained in a
on the uptake of REEs by fluorapatite and calc-silicates sealed gold capsule. All experiments were quenched in air and water,

Table 1. Summary of fluorapatite/melt partitioning experiments.

ZREE202 in T P Time
Series bulk (wt%) Pre-heating' (°C) (GPa) (h) Reference2

single-REE-substituted fluorapatite 3
D 0.03-0.04 above T 792-798 0.14-0.16 41-48 present
E 0.03-0.04 below T 788-793 0.14 336 present
B 0.03-0.04 above T 680-690 0.10-0.12 11-21 a, present
A 3.1-3.7 above T 685-700 0.10-0.12 1-48 a

binary-REE-substituted fluorapatite 4
3.3-3.5 above T 680-691 0.12-0.13 40-48 present, b

hexa-REE-substituted Iluorapatite 5
3.5 above T 684 0.12 39 present

Above T: charges heated to 890°C at about 0.17 GPa, then cooled at 0.1°/min to T; below
T: charges heated at 660-670°C at P for ~24 h, then temperature increased gradually to T.
2 (a) Fleet and Pan (1995b), series B were re-analyzed in present study because EPMA
operating conditions were not optimized for minor REE in previous study; (b) Fleet and Pan
(1997), X-ray structures on four crystal products.
3 La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu in series A, B, and D; La, Ce, Nd, Sm, Eu,
Gd, Er in series E.
4 La + Gd, Ce + Dy, Pr + Er, Nd + Yb, Sm + Lu, Eu + Lu, La + Lu, Ce + Yb, Pr +
Er, Nd + Dy, Sm + Er, Eu + Lu.
5La + Sm + Gd + Er + Yb + Lu.
 Partitioning of REEs in apatite and melt 4747

Table 2. Uptake of REE203by series D and E single-REE-substituted fluorapatites.

FAp 2 REE203in bulk REE203 in melt REE203in apatite D(REE: FAp/melt) D(REE: FAp/melt)
REE Expt I (nag) (wt%) (wt%) (wt%) experiment smoothed3

series D experiments
La AP64 1.9 0.027 0.024 0.13 (4)4 5.4 5.3
Ce AP65 3.7 0.029 0.023 0.18 (3) 7.8 7.3
Pr AP74 0.3 0.027 0.026 0.25 (3) 9.6 8.2
Nd AP72 2.8 0.030 0.024 0.19 (2) 7.9 8.4
Sm AP73 2.8 0.031 0.025 0.22 (3) 8.8 7.8
Eu AP66 1.7 0.030 0.027 0.17 (2) 6.3 6.7
Gd AP67 1.2 0.031 0.029 0.18 (2) 6.2 5.7
Dy AP68 2.7 0.030 0.028 0.10 (3) 3.6 3.9
Er AP69 2.1 0.032 0.031 0.08 (2) 2.6 2.5
Yb AP70 2.8 0.036 0.035 0.037 (18) 1.1 1.4
Lu AFTI 3.0 0.034 0.034 0.036 (11) 1.1 1.0

series E experiments
La AP81 12.0 0.027 0.015 0.10 (2) 6.7
Ce AP82 5.5 0.029 0.021 0.16 (2) 7.6
Nd AP84 2.4 0.030 0.025 0.19 (3) 7.6
Sm AP85 5 0.031 -- 0.16 (2) --
Eu AP86 7.7 0.030 0.020 0.13 (2) 6.5
Gd AP87 2.1 0.031 0.027 0.17 (4) 6.3
Er AP88 3.6 0.032 0.029 0.10 (2) 3.4

Experimental conditions: series D: AP64-AP66- 795°C, 0.14 GPa, 41 h; AP67-AP70- 792°C, 0.15 GPa, 46 h; AP71-AP74- 798°C, 0.16
GPa, 48 h. series E: APS1, AP85, AP87- 788°C, 0.14 GPa, 336 h; AP82, AP84, AP86, AP88- 793°C, 0.14 GPa, 336 h.
2 FAp is fluorapatite; total weight of products was ~ 9 0 mg.
3 See Figure 4.
4 Numbers in parentheses are estimated standard deviations (_ l~r), based on multiple analyses.
5 Yield indeterminate.

and capsule integrity was monitored by weighing. The experiments
are summarized in Table 1, and details are given below and in Tables
2 and 3.
For series D single-REE-substituted FAp, the charges were con-
tained in 3.5 cm gold capsules, preheated at 891YC and about 0.17
GPa, cooled at 0.1 deg.min -1 to the run temperature, and maintained
at about 790-800"C for 40-48 h. The products generally consisted
of either pieces (up to 0.3 × 0.3 × 2 mm 3) of a large single crystal
or several medium-sized crystals of FAp and quenched melt. Soluble
salts were removed from run products by digesting in hot water. The
FAp crystals were separated from the remaining quench products by
handpicking, washed in hot water, and weighed.
For binary(LREE + HREE)- and bexa-REE-substituted FAp, the
experiments closely followed those of the series A and B single-
REE-substituted FAp of Fleet and Pan (1995b). The charges were
contained in 4 cm gold capsules, preheated as above, and maintained
at temperatures of about 680-690°C and 0.12 GPa for 4 0 - 5 0 h.
The products consisted of a few fragments (0.1-0.2 mm in diameter
and 0.4-0.8 mm in length) of a large crystal of FAp, that had
evidently broken during quenching and processing of the quench
products, medium- and small-sized crystals of FAp, tmcharaeterized
quench phosphates, glass, NaF, and fluid, + cuspidine [Ca4Si2OT-
(F, OH)2]. Separate experiments showed that the large FAp crystals
were the first liquidus products to appear and grew at about 800°C.
Crystal growth of FAp was evidently initiated on the cooling gradient
in these experiments (and in series A and B of Fleet and Pan, 1995b,
and series D of this study as well; Table 1), and the extent of
annealing and/or recrystallisation at the lowest run temperatures
investigated (680-700"C) was unknown, but believed to have been
limited (cf. Fleet and Pan, 1995b).
For series E single-REE-substituted FAp, the charges were con-
tained in 3.5 cm gold capsules and preheated at 660-670"C for ~24
h. Temperature was raised gradually to the run temperature and
maintained at 788-793°C for 14 days. The products generally con-
sisted of either pieces (up to 0.6 × 0.6 × 1.4 mm 3) of a large single
crystal or several medium-sized crystals of FAp and quenched melt.
The FAp crystals were separated by digesting in hot water and hand-
picking, as in series D. The Sm-FAp product was in the form of
massive fine-scale acicular grains, and no attempt was made to sepa-
rate it from the quenched matrix.
The run products were analysed using a JEOL JXA-8600 Su-
perprobe, fitted with three automated wavelength-dispersion spec-
trometers, at the University of Saskatchewan. All quantitative analy-
ses of the apatite crystals were performed on sections parallel to the
c axis (Stormer et al., 1993), although some crystals were also
mounted and polished perpendicular to the c axis for detecting com-
positional zonation by backscattered electron (BSE) images. Op-
erating conditions included an accelerating voltage of 15 kV, a beam
current of 10 nA, beam diameter of 2 - 5 #m, 20 s counts (60 s for
Si and Na in FAp from series D and E experiments), and minerals
(Durango fluorapatite for Ca and P; quartz, Si; jadeite, Na; synthetic
fluorphlogopite, F) and synthetic REE phosphates as standards (Jar-
osewich and Boatner, 1991 ). The minor amounts of REEs in apatite
of series D and E were analysed at 25 kV, 20 hA, and 50 s. Fleet
and Pan (1995b) analysed all their synthetic FAp products at 15
kV, 10 nA, and 20 s, but HREEs in their series B products were
generally not detectable. Therefore, the series B apatites were re-
analysed in this study using 60 s counts for Si and Na (at 15 kV
and 10 nA), and 25 kV, 20 nA, and 50 s for REEs. It should be
pointed out that the microprobe analysis of REEs in our synthetic
fluorapatite, unlike natural REE-bearing minerals (Roeder, 1985),
was straightforward (i.e., using Lal peaks), because most of our
runs contained only a single REE. Also, the combinations of REEs
in the binary- and bexa-REE substituted experiments were selected
to avoid peak-overlaps using La~ peaks, except for Gd, for which
we used the L/~I peak. Durango fluorapatite was analysed routinely
to monitor the calibration for minor amounts of REEs, with the
following results for a total of sixty-two EPMA spot analyses: La203:
0.418(32) [0.414] wt%; Ce203: 0.512(41) [0.505]; Pr203:
0.060(15) [0.069]; Nd203: 0.148(12) [0.151]; Sm203: 0.016(5)
[0.019]; Eu203: 0.004(2) [0.006]; Gd:Oa: 0.041(12) [0.045];
Dy203: 0.020(8) [0.021]; Er203: 0.005(3) [<0.005]; Yb203:
4748 M. E. Fleet and Y. Pan

Table 3. Uptake of REE203 by synthetic fluorapatites annealed at 680-690°C.

REE203 REE203 REE203 REE203

in bulk in apatite ~ D(REE: in bulk in apatite D(REE:
REE Expt (wt%) (wt%) FAp/mt) 2 REE Expt (wt%) (wt%) FAp/mt)

series B single-REE-substituted FAp 3 binary(LREE + HREE)-substituted FAp4

La API9 0.027 0.13 (3) 4.8 La AP49 1.590 4.83 (37) 3.0
Ce AP36 0.029 0.18 (5) 6.2 AP55 1.584 5.28 (41) 3.3
Pr AP37 0.027 0.19 (5) 7.(l Ce AP50 1.574 5.21 (39) 3.3
Nd AP24 0.030 0.21 (2) 7.0 AP56 1.635 5.96 (60) 3.7
Sm AP38 0.031 0.16 (8) 5.2 Pr AP51 1.576 5.98 (35) 3.8
Eu AP21 0.030 0.14 (3) 4.7 AP57 1.567 5.50 (15) 3.5
Gd AP22 0.031 0.16 (2) 5.2 Nd AP52 1.979 7.79 (60) 3.9
Dy AP40 0.030 0.12 ( 1) 4.0 AP58 1.649 6.30 (23) 3.8
Er AP25 0.032 0.09 (2) 2.8 Sm AP53 1.602 5.79 (48) 3.6
Yb AP26 0.036 0.06 (2) 1.7 AP59 1.596 5.62 (30) 3.5
Lu AP20 0.034 0.03 ( 1) 0.9 Eu AP54 1.678 5.88 (28) 3.5
Gd AP60 1.722 5.76 (24) 3.3
hexa-REE-substituted FAp5 AP49 1.760 4.98 (161 2.8
Dy AP50 1.759 2.86 (10) 1.6
La AP46 0.554 1.70 (5) 3.1
AP58 1.772 4.02 (12) 2.3
Sm AP46 0.512 1.78 (29) 3.5
Er AP51 1.753 2.06 (19) 1.2
Gd AP46 0.580 1.63 (19) 2.8
AP57 1.750 2.25 (69) 1.3
Er AP46 0.596 (/.48 (8) 0.8
AP59 1.772 2.30 (19) 1.3
Yb AP46 0.592 0.29 (8) 0.5
Yb AP52 1.466 0.99 (9) 0.7
Lu AP46 0.621 (I.25 (8) 0.4
AP56 1.739 1.76 (76) 1.0
Lu AP53 1.837 0.89 (68) 0.48
AP54 1.849 1.03 (8) 0.56
AP55 1.871 0.88 (111 ) 0.47
AP60 1.792 1.22 (25) 0.68

Numbers in parentheses are estimated standard deviations (_+ l~r), based on multiple analyses.
2 FAp is fluorapatite, mt is melt.
3 Experimental conditions: Fleet and Pan (1995b).
4 Experimental conditions: AP49-AP52- 680°C, 0.12 GPa, 48 h; AP53-AP56- 684°C, 0.12 GPa, 40 h; AP57-AP60- 691°C, 0.13 GPa, 40 h.
5 Experimental conditions: 684°C, 0.12 GPa, 39 h.

0.005(3) [0.006]; and Lu203: 0.000(2) [0.004], where standard
deviations ( _+ la) are in parentheses, and comparable EPMA results
of Roeder et al. (1987) are in square brackets. The REE contents
reported for FAp in Tables 2 and 3 are averages of at least ten to
twelve individual spot analyses of the largest crystal(s) from each
experiment. Other compositional details are given in the Appendix.
Very weak sector zoning is evident in some BSE images, but the
associated variation in REE content is insignificant. Fluorapatite
grains from series D and E experiments are homogeneous. Fluorapa-
tite grains from all other experiments have a broad (core) region of
homogeneity, and many have a margin (or rim) of slightly different
composition. Grains of Pr-FAp have a slightly REE-rich core, which
we attribute (below) to the PrCl3" 6H20 starting material. A weak
oscillatory growth zoning attributed to variation in REE content is
sometimes evident in BSE images also. The EPMA data in Tables
2 and 3 are averages of all composition regions of the FAp grains
analysed, except for rims that are clearly quench products.
3. DISCUSSION
3.1. Uptake of REEs by Fiuorapatite from Phosphate-
Fluoride Melts
The uptake of REEs by fluorapatites synthesized in the
present study and Fleet and Pan (1995b) (single-REE-substi-
tuted FAp, series D and B with minor and series A with
major contents of substituents, and binary(LREE + H R E E ) -
and hexa-REE-substituted FAp; Table 1 ) is represented in
Figs. 2 and 3. We believe the largest apatite crystals repre-
sented the ]iquidus phase in each of the experiments and
crystallized from melt under near equilibrium conditions,
even though many of the experiments were continued to
much lower temperatures. The phase relations in the CaO-
P205-NaF-H20 system do not appear to have been investi-
gated, but the fluorapatite liquidus extends down to 675°C at
0. l GPa in the Ca3 (POa)2-CaFz-H20 system (Biggar, 1962;
Wyllie, 1967), and we would expect somewhat lower liq-
uidus temperatures with NaF added. Although there were
numerous melt inclusions in the large fluorapatite crystals,
fluid inclusions were absent. This suggests that liquidus
melts were not saturated with respect to water and other
volatiles.
The assumption of near-liquidus character for the largest
apatite crystals is consistent with the series D experiments
on single-REE-substituted FAp, which were annealed at and
quenched from high temperature ( 7 9 0 - 8 0 0 ° C ) yet yielded
REE contents closely comparable to those of the largest
apatite crystals of corresponding series B experiments of
Fleet and Pan ( 1995b; quenched from 6 9 0 - 7 0 0 ° C ; Tables
2 and 3). Preliminary experimentation established liquidus
temperatures for series D bulk compositions of about 8 0 0 -
810°C . Yields of FAp varied from 0.3 mg for Pr-FAp
(AP74; Table 2) to 3.7 mg for Ce-FAp (AP65), and repre-
sented only 0 . 3 - 4 . 1 % crystallization of the melt, respec-
tively.
The melt phase was not quenchable, and this frustrated
 Partitioning of REEs in apatite and melt 4749

0.9
0.03

0.8

0.7
-I

0.6
t/J
¢..
O
°m - 0.0 []
(U 0.5 0.0 0.03
O
V

0.4
• A, single-REE
+
[] binary-REE
t~ 0.3 + hexa-REE
z
0.2 inset
+ B, single-REE
x D, single-REE
0.1 • E, single-REE

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Total REE (cations pfu)

Fig. 2. Substitution of REEs in synthetic fluorapatite (FAp), showing close approach to Na+Si = ZREE (reference
line), consistent with the formula Cat0_x_2yNayREEx+y(P~.xSixO4)6F2:results for series A single-REE-substituted FAp
are from Fleet and Pan (1995b); note that, for minor amounts of REEs (inset), Na+Si tends to exceed ZREE, as in
some natural apatites (e.g., Roeder et al., 1987); experimental conditions and combinations of REEs investigated are
summarized in Table 1, and details of FAp compositions are given in the Appendix.

determination of detailed phase relations and melt composi-
tion at the temperature of final crystallization. However, FAp
was the only equilibrium solid phase in series D and E
experiments, and the equilibrium solids at the lowest temper-
atures investigated in other experiments (680-700°C) com-
prised FAp, of lower REE content than reported in Table 3,
___cuspidine _ NaF.
Moreover, quantitative mechanical separation of liquidus
FAp crystals from quench products was possible in series D
and E experiments. This permitted the final content of
REE203 in the melt (REEMelt) to be calculated directly by
subtracting the REE203 lost to liquidus FAp from the bulk
(starting) composition (Table 2), using the formula
REEM,It = [ (REEaulk × WtBulk)
-- (REEFAp X WtFAp)]/(WtBulk -- WtFAp),
where REEsu~k and REEFAp are the contents of REE203 in
the bulk composition and FAp, respectively, and Wtbu~, and
WtFAp are the weights of starting composition ( ~90 mg) and
FAp recovered (Table 2), respectively. The reduction in
REE203 content of the melt due to crystallization of FAp
was insignificant for HREEs and ranged up to about 20%
for Ce, Nd, and Sm. For the remaining experiments,
binary (LREE + HREE)- and hexa-REE-substituted FAp and
series A and B single-REE-substituted FAp (Fleet and Pan,
1995b), we presently assume that the REE203 content of
the melt coexisting with the largest FAp crystals was approx-
imately the same as the bulk composition. However, LREE
contents would have been somewhat lower in melts than
corresponding bulk compositions because they behaved
compatibly with respect to FAp in all experiments.
Inhomogeneity of the FAp crystals analysed was minimal,
as indicated by standard deviations of multiple analyses
(e.g., Tables 2 and 3). The compositional fluctuation due to
sector zoning was also minimal (Fleet and Pan, 1997) and
did not signal significant nonequilibrium intercrystalline and
intracrystalline partitioning through local equilibria at
growth surfaces (cf. Rakovan and Reeder, 1994).
In all compositional series investigated, the concentration
of REEs in FAp is related to concentration in the melt (Fig.
3) and peaks at (or near) Nd for 0.03-0.04 wt% bulk
REE203 (series D and B) and binary(LREE+HREE)-sub-
stituted FAp, at Sm for hexa-REE-substituted FAp (experi-
ment AP46 with La, Sm, Gd, Er, Yb, Lu), and at Nd "-* Sm
for single-REE- substituted FAp with 3.1-3.7 wt% bulk
REE203 (series A; Fleet and Pan, 1995b). The REE uptake
curves are symmetrical about the maximum value, with the
uptake of La in any composition series being appreciably
greater than that of Lu: the La/Lu ratio is 3.6 in series D,
4.3 in series B, and 3.1 in series A single-REE-substituted
FAp, 5.0 in binary (LREE+HREE)-substituted FAp, and 6.8
in hexa-REE-substituted FAp.
The uptake curves generally vary smoothly through the
4750 M.E. Fleet and Y. Pan

0.3 , • , . ~ • , . , . , • ,
were not buffered for oxygen fugacity, but the starting com-
a) positions and experimental procedures clearly define fo2
within the field of magnetite stability. Fleet and Pan (1995a)
series D suggested that REE abundance above the smooth arched
0.2
curve through the values for REE 3÷ with spherically-sym-
metrical 4 f electron states (La 3÷, Gd 3÷, Lu 3+) reflected a
W
weak 4fcrystal-field contribution. However, the present up-
n- 0.1 take values are not consistent with this interpretation.
Normalization of the REE abundance in FAp by the melt
composition (Fig. 4) yields partition coefficients that are
i , i , I , i essentially independent of the concentration of individual
0.0
La Ce Pr Nd PmSmEu Gd Tb Dy Ho Er Tm Yb Lu REE for the major-to-minor element ranges of series A sin-
gle-REE-substituted FAp and binary(LREE+HREE)- and
0.3 hexa-REE-substituted FAp, but are higher for the minor ele-
b) ment ranges of series D and B. The good internal agreement
of the D (REE:FAp/melt) values for the major-to-minor ele-
series B
0.2
ment substitutions may be an artifact of a group substitution
effect for the binary(LREE+HREE)- and hexa-REE com-
positions. We note that the total REE substitution in these
6
u~ fluorapatites was similar to that of the series A single-REE-
ILl 0.1
~Y substituted FAp, so that, in any given FAp, other REEs may
have contributed significantly to nonideal mixing on the Cal
and Ca2 sites. A non-Henrian character for partitioning in
L • i . i . i . i . i . i . 1 the REE-FAp-melt system (Fig. 4) is also indicated by the
0.0
La Ce Pr Nd PmSmEu Gd Tb Dy Ho Er Tm Yb Lu limited solid solution of the britholite component in FAp. In
experiments on single-REE-substituted FAp with 50 tool%
14 of the britholite component (series C experiments of Fleet
12
c) and Pan, 1995b), the products were varied and nonsystem-
single-REE FAp
atic through the 4ftransition-metal series, and the uptake of
lO REEs by FAp did not extend significantly beyond the
amounts for corresponding experiments of series A with
° just 10 mol% of the britholite component in the starting
u7 8 composition,
LU
O~ 4

- , • , • , - , • i • i • i

10 ×

9 x
La Ce Pr NdPmSmEu Gd Tb Dy Ho Er TmYb Lu
7 ×
Fig. 3. Uptake of REEs by fluorapatite (FAp) from H20-bearing
_ 6
phosphate-fluoride melts: (a) minor abundances in series D single-
REE-substituted FAp (Table 2); (b) minor abundances in series B |
D.
5 • •

single-REE-substitutedFAp (Table 3); c) major and minor abun-

dances; open-squares are binary(LREE+HREE)-substituted FAp s
(Table 3), filled squares are hexa-REE-substitutedFAp (Table 3), 2
and filled circles are single-REE-substitutedFAp (Fleet and Pan,
1995b). Error bars are ± 1~, based on multiple analyses.
0 i , i , i , i , i i i , i , L

La CO Pr Nd PmSmEu Gd Tb Dy Ho Er Tm Yb Lu

maximum value, within analytical error (cf. error bars for Fig. 4. Melt-normalized REE contents of ftuorapatite (FAp):
crosses are series D single-REE-substitutedFAp with minor contents
multiple analyses in Fig. 3). The relatively lower abundance
of REEs (Table 2); filled squares are series B single-REE-substituted
of Ce and Pr in series A single-REE-substituted FAp is FAp with minor contents of REEs (Table 3); filled circles are
attributed to the influence of starting composition at high binary(LREE+HREE)-substituted FAp (Table 3); open squares are
REE content (Fleet and Pan, 1995b): CeF3 for Ce-FAp and hexa-REE-substitutedFAp (Table 3 ); and pluses are series A single-
PrCI3-6H20 for Pr-FAp. Also, for single-REE-substituted REE-substituted FAp (Fleet and Pan, 1995b). Bulk compositions
have been used for melts of binary- and hexa-REE and series B and
compositions, Pr-FAp has a lower liquidus temperature, as A single-REEexperiments;therefore, D(REE:FAp/melt) values are
inferred from the lower yield of FAp in series D (Table 2), overestimated for Pr-FAp to Sm-FAp by up to 20% for series B and
and the core of fluorapatite crystals is anomalously enriched 10% for binary- and hexa-REE and series A single-REE experi-
in Pr. All REEs presently investigated were dominantly in ments. The anomalouslyhigh value for series D Pr-FAp is attributed
to PrC13"6H20 starting material (see text). Other divergence from
the trivalent state. Anomalies in the uptake curves at Ce and
a smoothed trend for series D (small filled circles) is within analyti-
Eu, consistent with significant amounts of Ce 4÷ and Eu 2÷, cal and experimental uncertainty; the trend shown has been fitted
respectively, are not evident. Our hydrothermal experiments visually.
 Partitioning of REEs in apatite and melt
In the present synthetic fluorapatites, trivalent REEs sub-
stitute for divalent Ca and valence compensation is made
largely by substitution of Na and Si for Ca and P, respec-
tively, as in the following:
REE 3+ + Si 4+ = C a 2+ + ps+;
Calo-xREEx(PI.~SixO4)6A2 ( 1)
REE 3+ + Na l+ = Ca2+; Calo.2yNayREEy(PO4)6A 2 (2)
(e.g., Watson and Green, 1981; Rtknsbo, 1989; Fleet and
Pan, 1995b). Substitution of major amounts of REEs closely
approaches the combined formula Calo.x-2yNayREEx+y-
(Pl.xSixO4)tF2, with Na+Si ~ YREE, as shown in Fig. 2
(cf. Roeder et al., 1987). These coupled substitutions place
additional constraints on mixing in fluorapatite solid solu-
tions. The difference in partition coefficients between minor-
and major-element experiments is not unexpected because
of the compositional difference (i.e., Si) between these ex-
periments and the involvement of Si in the heterovalent sub-
stitution of REEs for Ca as a charge-balance mechanism (cf.
Lundstrom et al., 1994; Gaetani and Grove, 1995; Blundy
et al., 1996). In addition, other minor substitutions, possibly
involving departures from ideal stoichiometry, might exert
significant influence on the uptake of minor amounts REEs
by FAp. For the minor-element experiments, the sum of
Na+Si tends to exceed EREE in FAp (Fig. 2), as in some
natural apatites (e.g., Roeder et al., 1987). Error in the deter-
mination of low abundances of Na and Si by EPMA undoubt-
edly contributed to these discrepancies, but the largest disce-
pancies consistently correlate with excess Na (Appendix).
We emphasize that the significant difference in partition
coefficients between minor- and major-element experiments
does not reflect error in estimation of melt compositions
for the latter. This error does systematically reduce
D(REE:FAp/melt) values for experiments with LREEs, but
only by up to about 10% for yields of liquidus FAp similar
to those of series D experiments with minor abundances
of REEs (cf. Table 2 and Fig. 4). For all major-element
experiments, binary (LREE +HREE), hexa-REE, and single-
REE series A, partition coefficients have been calculated
using compositions for the largest FAp crystals, which were
the liquidus phase and represented crystallization of only a
small fraction of the Ca phosphate component of the melt.
Also, partition coefficients are considerably reduced for ma-
jor abundances of REEs (by ~50%; Tables 2 and 3), thus
minimising the effect of loss of REFaO3 to FAp on the melt
composition.
The results for series D experiments (Table 2) are seem-
ingly more appropriate for modelling the fractionation of
minor amounts of REEs in natural fluorapatite. In these con-
trolled experiments, the REE contents of FAp were just
0.04-0.25 wt% REFaO3 and closer to the composition of
common apatite. Moreover, only a small fraction of the melt
(0.3-4 wt%) and the Ca phosphate component in the melt
( 3 - 9 wt%) had crystallized. Therefore, the final REE con-
tents of the melt were little changed from the bulk composi-
tion and were estimated with some confidence by subtracting
the REEzO3 lost to FAp from the starting composition. Pre-
ferred values of D(REE:FAplmelt) have been obtained by
4751
smoothing the series D results (Table 2; Fig. 4), recognizing
that the high value for Pr203 in the series D experiment
AP74 is attributable to the effect of Pr starting material.
The estimated errors in these smoothed D(REE:FAp/melt)
values are __.20% for LREE and +__30% for HREEs and are
based largely on uncertainty of FAp composition. Error in
determination of the proportion of liquidus FAp was not the
principal source of error in D(REE:FAp/melt). As noted
above, in series D experiments, liquidus FAp crystals were
readily separated from other washed products using a binoc-
ular microscope and microforceps. Significant error in the
weight of liquidus FAp recovered was unlikely. Also, even
a very large error of 50% in weight of liquidus FAp would
contribute only about ___10% to the uncertainty in the parti-
tion coefficient for experiments with high D(REE:FAp/
melt) values and high yields of FAp (e.g., APT2, Table 2).
Error in the bulk (starting) composition, which was prepared
from reagents that were carefully weighed and mixed, was
conservatively within ___5% for the minor abundances of
REEs in these experiments.
Reversal of REE partitioning between apatite and melt or
fluid has been established in two previous studies, through
diffusion of REEs in apatite at 1120°C, 0.75 GPa, and 14
days (Watson and Green, 1981) and re.crystallization of
REE-bearing apatite at 1000*C, 1.0 GPa, and 93-100 h
(Ayres and Watson, 1993). The concern in this study was
that FAp might crystallize metastably in series D experi-
ments and in other experiments preheated above the liquidus
temperature. A high preheating temperature was desirable to
ensure complete reaction and homogenization of the starting
materials, particularly of REE203. In series E experiments,
the charges were preheated significantly below the experi-
mental temperature, without homogenizing the starting com-
position, thus promoting disequilibrium crystallization of
REE-bearing FAp, other Ca phosphates, and cuspidine, and
annealed for 14 days at the run temperature (Table 2). The
yields of FAp were nonsystematic and generally greater than
in series D experiments, and the crystal products were varied,
complicating estimation of the final REE content in the melt.
The greater yields are attributable to the somewhat lower
experimental temperatures; 788°C for AP81, AP85, and
AP87, and 793°C for AP82, AP84, AP86, and AP88. The
7880C experiments were performed in the same reaction
vessel and furnace as series D (and of all prior experiments),
and, therefore, the precision of temperatures is very high
(__ I°C), whereas the latter group were performed in a differ-
ent vessel and furnace. An experiment on Pr-FAp (AP83)
failed, and the Sm-FAp product was too fine grained to
separate from quench products for weighing. The REE con-
tents of series E FAp are closely comparable to the corre-
sponding products of the series B experiments of Fleet and
Pan (1995b), and the D(REE:FAp/melt) values are all in
good agreement (within + ltr) with the corresponding
smoothed values for series D experiments (Tables 2 and 3 ).
All grains of series E FAp analysed were homogeneous from
core to margin, demonstrating that all early unequilibrated
FAp products had completely recrystallized and homoge-
nized.
The present coefficients for partitioning of REEs between
FAp and depolymerized phosphate melts at major REE abun-
 4752 M.E. Fleet and Y. Pan

dances are within the range of values for partitioning be-
tween FAp and tholeiitic andesite/basanite melts at 0.75-
2.0 GPa, 950-1120°C , and 0.2-2.8 wt% REE203 in FAp
(Watson and Green, 1981 ). However, the REE patterns for
our experiments peak earlier in the 4ftransition-metal series
and have higher La/Lu [or D(La)/D(Lu)] ratios. The latter
discrepancy may be attributable to the higher F contents of
our experiments; e.g., HREE-F complexes are predicted to
have greater stability than LREE-F complexes in aqueous
fluids (Wood, 1990; Haas et al., 1995). The present partition
coefficients are also broadly comparable to those calculated
for early fiuorapatite in the Skaergaard layered series (Fig.
1 ) although, again, the D(La)/D(Lu) ratios are greater than
in nature.
The relevance of the present partitioning experiments to
natural assemblages may be questioned in view of the
marked difference in composition between phosphate-fluo-
ride melts and basic silicate melts. However, Ca and REEs
are strongly coupled to phosphate in basic silicate melts
(Ryerson and Hess, 1980; see also, Beswick and Carmichael,
1978; Frey et al., 1980; Jolliff et al., 1993), and the addition
of P205 polymerizes complex synthetic silicate melts by
complexing with the network-modifying cations (Ryerson
and Hess, 1980; Mysen, 1988). Thus, in basic silicate melts,
REEs are expected to be preferentially complexed as discrete
alkali and alkaline earth orthophosphate entities, just as they
are in the present phosphate-fluoride melts.
merits in Fig. 4). These observations suggested that the over-
all site preference for REEs [(REE-Ca2/REE-Cal) >1] is
determined by equalization of bond valence but the effective
size of the Ca positions exerts greater control on the selectiv-
ity of apatite for REEs (i.e., the form (or shape) of the melt-
normalized REE pattern). This interpretation was developed
and applied to calc-silicate minerals in Fleet and Pan
(1995b) and Pan and Fleet (1996b).
There is some ambiguity in defining the effective size of
the Ca positions in apatite because the coordination of Cal
is really (6 + 3) rather than 9, and Ca2 is bonded to 6 O
and 1 F (in FAp). Thus, any simple analysis of the spatial
accommodation of REEs in the apatite structure involves
approximation and compromise. For Cal, we presently com-
pare the effective REE-O bond distance, calculated using
effective ionic radii of REE 3+ for ninefold coordination with
oxygen (Shannon, 1976), with the mean Cal-O bond dis-
tance for the CalO9 polyhedron in fluorapatite, hydroxylapa-
rite, and chlorapatite (FAp, OHAp, and ClAp, respectively;
Hughes et al., 1989). For Ca2, we compare the effective
REE-O bond distance, calculated using ionic radii for sev-
enfold coordination with oxygen (values for Pr, Nd, Ho,
Tm, and Lu are interpolated) with the mean of the six Ca2-
O distances, recognizing that there are actually seven anions
in the Ca2 polyhedron (Fig. 5; Hughes et al., 1989).
Comparing the structures of FAp, OHAp, and ClAp, sub-

3.2. Crystal-Chemical Controls on REE Uptake by

Fluorapatite a)
6 0.0
The two Ca positions in the structure of apatite have dis-
tinct stereochemistries [ Ca 1, equipoint 4 ( f ) , site symmetry O
v
=
3, CaO9 polyhedron; Ca2, equipoint 6(h), site symmetry m, o:
CaO6A (A = F,OH,CI) polyhedron]. Bond valence has been 0.1
used extensively to understand the site preference of REEs sitefluorapatit
_ Cea`?.
in apatite and calc-silicate minerals (Hughes et al., 1991; o and
Fleet and Pan, 1995a, 1995b; Pan and Fleet, 1996b). It is a hydroxylapatite
measure of the bonding power of an atom and is calculated 0.2 = . L . i . = . , . i , i , i

using empirical bond strength-bond length correlations (cf. La Ce Pr bid PmSm Eu Gd Tb Dy Ho Er Tm Yb Lu

Brown, 1981 ). Ca2 is the only Ca position coordinated to the

volatile anion component (F, OH, CI) and is underbonded in i • , • i • v - i • i • , - i

endmember fluorapatite. Therefore, Fleet and Pan (1995a) b)

suggested that minor amounts of trivalent REEs should favor 6 0.0
Ca2 over Cal, to increase the bond valences of both Ca2
and F, and Na should then favor Cal. Hughes et al. (1991) ?
used calculated bond valence to show that HREEs (Gd o
Lu) are underbonded in either Ca position, whereas, La, Ce, +~ 0.1
and Pr are slightly overbonded in the Cal position and, CaI sitechlorapatite ~~"-~
therefore, should prefer Ca2, Pm and Sm should favor Cal, o
and Nd should readily substitute into either Cal or Ca2.
These results suggested that bond valence might influence 0.2 , . , . , . , . , . , . J . l

both REE site preference and selectivity of apatite for REEs. La Ce Pr Nd PmSm Eu Gd Tb Dy Ho Er Tm Yb Lu

However, the X-ray structure refinements of Fleet and Pan
(1995a) revealed an apparent monotonic decrease in REE
site occupancy ratio (REE-Ca2/REE-Cal) through the 4 f
transition-metal series, with the bond valences of Cal and
Ca2 remaining more or less equal. In contrast, the melt-
normalized REE pattern for these synthetic fluorapatites was
peaked near Nd --, Sm (e.g., series A single-REE experi-
Fig. 5. Effective REE--O bond distances (R3+--O; calculated
using effective ionic radii of Shannon, 1976) compared with mean
Ca--O bond distances ((Ca--O)) in: (a) fluorapatite (FAp) and
hydroxylapatite (OHAp) and (b) chlorapatite (ClAp). Crystal struc-
ture data are from Hughes et al. (1989); [91R3+--O are compared
with (Cal--O) (filled circles), and [71R3+--O with (Ca2--O)
(open squares). Note that data for the Ca2 site of ClAp (b) decrease
monotonically through the 4 f transition-metal series.
 Partitioning of REEs in apatite and melt 4753

stitution of the volatile anion component has essentially no
influence on the size of Cal (e.g., the mean Cal-O distances
are 2.554, 2.553, and 2.549 .~, respectively, Hughes et al.,
1989). However, the Ca2 site is directly affected by the
volatile component and is considerably enlarged and dis-
torted by the introduction of C1; the mean Ca2-O distances
are 2.463, 2.461, and 2.493 .~, respectively (Hughes et al.,
1989). Individual Ca2-O distances do vary markedly and
differentially from FAp to ClAp, with Ca2-O1 increasing by
7.4% and Ca2-O2 decreasing by 2.9%. Also, although the
mean Ca2-O distances of FAp and OHAp are similar, indi-
vidual distances also exhibit significant variation and Ca2-
OH > Ca2-F (2.385 and 2.311 A, respectively). Figure 5
shows that, amongst REE 3+ cations, Nd would fit most
readily in Ca1 of FAp and OHAp, Nd -, Sm most readily
in Cal of ClAp, Ce-Pr most readily in Ca2 of FAp and
OHAp, and La most readily in Ca2 of ClAp. Recognizing
that LREEs and MREEs preferentially enter Ca2 of fluora-
patite, minimization of local strain at Cal and Ca2 appears
to be an adequate explanation for the present uptake patterns
for REEs in fluorapatite crystallized from H20-bearing phos-
phate-fluoride melts (Figs. 3, 4).
As further confirmation for a significant control by spatial
accommodation on selectivity of REEs, Fleet and Pan
(1997) reported profound change in the accommodation of
ylapatite; Wright et al., 1984; Grandjean-Lrcuyer et al.,
1993).
Data from both natural rocks and laboratory experiments
show that melt-normalized REE patterns of fluorapatite in
igneous systems are characteristically convex upward and
are crested near Nd --, Sm (Fig. 1 ). Figure 6a shows that
fluorapatite in metamorphic rocks is characterized by convex
upward REE patterns with maxima at Nd --, Sm. It is well
established that the shale-normalized REE patterns of cono-
dont apatites (carbonate-fluorapatite and carbonate-hydrox-
ylapatite) are characteristically convex upward and crest at
Sm -, Gd (Wright et al., 1984; Grandjean-Lrcuyer et al.,
1993), again pointing to a crystal-chemical control. Al-
though numerous analyses of REEs exist for fluorapatite of
hydrothermal origin (e.g., Raimbault et al., 1993; Pan and
Fleet, 1996b), most of these data are difficult to evaluate
for REE selectivity because of the lack of knowledge on the
REE compositions of coexisting fluids. The migmatitic gar-
net amphibolites of the Catalina Schist, California, under-
went fluid-rock interaction in a paleosubduction zone, and
their whole-rock REE compositions have been interpreted
to have derived from H20-rich fuids in equilibrium with
i i i i i i i i i i i i i i i

REEs by the apatite structure in the vicinity of Nd in the 4 f 60

transition-metal series. Unlike many other crystal-chemical
parameters for the single REE-substituted fuorapatites of ,t 5o
0
Fleet and Pan (1995a), the Cal-O1, Ca2-O1, P-O1, and P- 2
.,., 40
0 2 bond distances and O1-P-O2 bond angle did not vary
0
e-
monotonically through the 4ftransition-metal series, but had 30
distributions hinged at Nd.
20

O
3.3. Role of Volatile Components == ~o o

The foregoing crystal-chemical discussion suggests that i i i i i i i i i l i i i i i

the form of melt(or fluid ) -normalized REE patterns of natu-

La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
ral apatites is largely controlled by the dominant volatile
anion substituent. Briefly, melt(or fluid)-normalized REE = i i i i i | w i i w i i i i

patterns for fluorapatite and hydroxylapatite are expected to 5

be convex upwards (ignoring possible redox control on up- 712~ b)
take of Eu) and peaked in the vicinity of Nd -, Sm, with _~: 4
details depending on substituents, and, for chlorapatite, more 2
LREE-enriched.
These predictions are consistent with data for synthetic ¢-

and natural fluorapatite, hydroxylapatite, and chlorapatite. 2

We suggest that the small discrepancies in form between
patterns for the present synthetic FAp (Fig. 4) and those of
natural FAp (e.g., Fig. 1) are attributable to variation in
composition of the latter, but confirmation will require more
information on the crystal structures of the natural apatites
as well as more accurate chemical analysis for F and H20.
The relative error in the conventional EPMA determination
of F in apatite, alone, can be considerable (Stormer et ai.,
1993), and could well obscure a subtle control of composi-
tion on both selectivity for REE and REE uptake. Also, most
published data on REEs in natural apatites are for fluorapatite
(Fleischer and Altschuler, 1986) and biogenic/diagenetic
apatite (mainly carbonate-fluorapatite or carbonate-hydrox-
0 i i i i i i i i i i i i i J I
La Ce Pr Nd Pm Srn Eu G~I Tb Dy Ho Er Tm Yb Lu
Fig. 6. REE patterns of (a) fluorapatite from metamorphic rocks
normalized to host rocks (sample 642 is from an amphibolite zone;
135, clinopyroxene-in zone; and 198, orthopyroxene-in zone; data
from Bingen et al., 1996; the anomalous behaviour of Sm is likely
an analytical artifact; sample G072 is from an orthopyroxene-in
zone; data from Pan and Fleet, 1996a); (b) apatite from migmatitic
garnet amphibolites of the Catalina schist, normalized to host rocks
(data from Sorensen and Grossman, 1989).
4754
subducted sediments (Sorensen and Grossman, 1989). Fig-
ure 6b shows that the host-rock-normalized REE patterns of
apatite (fluorapatite or hydroxylapatite?) in the migmatitic
garnet amphibolites are convex upward and are crested at
Sm ~ Tb, again consistent with crystal-chemical prediction.
The melt-normalized REE pattern for apatite in natural
spinel lherzolites from Yemen (Chazot et al., 1996) is shown
in Fig. 7. Ca-rich clinopyroxene (cpx), amphibole, and apa-
tite are the important carders of REEs in these lherzolites,
and the apatite is Cl-rich (with up to 4.35 wt% C1). The
REE composition of the coexisting melt has been calculated
after Chazot et al. (1996), from the observed D(REE:apat-
ite/cpx) and experimental D(REE:cpx/melt), using the
smoothed average results of Grutzeck et al. (1974) and Hart
and Dunn (1993). D(Lu) diverges from a smooth curve
through the 4 f transition-metal series and clearly reflects
analytical error. This melt-normalized REE pattern (Fig. 7)
is in good agreement with our prediction for chlorapatite.
Also, Boudreau and McCallum (1990) reported that primary
chlorapatite in the J-M Reef of the Stillwater Complex is
characteristically LREE enriched. Drinkwater et al. (1990)
reported that postcumulus apatites in the Dufek intrusion of
Antarctica show coupled enrichment in C1 and LREEs rela-
tive to their F-rich, cumulus counterparts. There are limited
REE data on chlorapatite from metamorphic/hydrothermal
environments. Lieftink et al. (1994) reported that the chon-
drite-normalized REE patterns of chlorapatite crystallized
from a high temperature Cl-bearing fluid are convex upward.
However, the REE pattern of the Cl-bearing fluid may be
distinctly different from that of C1 chondrite used in the
normalization.
Whereas apatite crystal chemistry (dominantly spatial ac-
commodation) appears to control the form of melt(or fluid)-
normalized REE patterns, the chemistry of REEs in the melt
(or fluid), and other physicochemical parameters, may exert
greater control on REE uptake. The correlation of REEs with
P in magma is well known (e.g., Beswick and Carmichael,
1978; Frey et al., 1980; Jolliff et al., 1993). Several studies
(Watson, 1976; Watson and Green, 1981; Ellison and Hess,
10
9 we presently compare D (REE:apatite / glass ) with the weight
8 ratio H20/FeF3 in the starting composition (as an approxi-
7 mation to f H 2 0 / f H F ; Fig. 8). Evidently D(REE:apatite/
W
m
4
° natural REE:fluorapatite/melt ratios (Fig. 1 ). We recognize
i . i . i . i . i . i . i .
La Ce Pr NdPmSmEu Gd Tb Dy Ho Er TmYb Lu
Fig. 7. REE:apatite/melt partition coefficients for chlorapatite
from spinel lherzolites from Yemen (open squares; Chazot et al.,
1996; see text for calculation of melt abundances) compared with
smoothed partition coefficients for series D single-REE-substituted
FAp with minor contents of REEs (filled circles). Note that the
pattern for the chlorapatite is La, Ce, Pr-enriched and that for the
synthetic fluorapatite is La, Ce-depleted.
M.E. Fleet and Y. Pan
1989) have demonstrated dependence of D(REE) on melt
polymerization, and Lesher (1986) has shown dependence
on thermal (Soret) diffusion. However, the REE-enrichment
factors from these experiments are too small to account for
the variation in natural REE:apatite/melt ratios, which is
greater than 2 orders of magnitude (Fig. 1 ). The high values
of D(REE:FAp/melt) for the peralkaline Ilfmaussaq intru-
sion (R~bnsbo, 1989; Larsen, 1979) and the similar values
for the Skaergaard layered series (Paster et al., 1974) and
granodiorite from the Peninsular Ranges batholith (Gromet
and Silver, 1983) indicate that melt polymerization is not a
single controlling factor. The influence of volatile compo-
nents (F, CI, H20) on REE solubility in silicate melts has
not been investigated in the present context. Jolliff et al.
(1993) did suggest that C1 content could be of significance
for apatite crystallized from lunar basaltic magma but con-
cluded that the key factor determining the REE concentration
in lunar apatite was the halogen/P ratio of lunar melts that
controlled the appearance of whitlockite, a complex Ca,Mg,-
Fe,Na,REE phosphate.
D(REE:apatite/melt) values for apatite-whitlockite-bear-
ing lunar rocks and meteorites are extremely low (present
Fig. 1; Jolliff et al., 1993; Lundberg et al., 1988). The most
significant feature of lunar basaltic magma, in the present
context, is the absence of H20, Jolliff et al. (1993) suggested
that this absence of H20 couples with D(REE:apatite/melt)
by elevating magma temperature. However, increase in tem-
perature alone would not change the partitioning of REEs
from compatible with respect to apatite to incompatible. Ad-
ditionally, the temperature of crystallization of the Yemen
apatite, for which D(REE:apatite/melt) > 1 (Fig. 7), must
be comparable to that of lunar apatite, although we recognize
that the primary nature of apatite in other peridotites has
been questioned (Frey et al., 1980).
The groundbreaking experiments of Watson and Green
(1981) are often cited as evidence for the control of melt
polymerization and temperature on partitioning of REEs be-
tween apatite and silicate melts (e.g., Jolliff et al., 1993;
Chazot et al., 1996). Watson and Green ( 1981 ) investigated
a broad range of melt composition (basanite and tholeiitic
andesite to granite), temperature (950-1120°C), and pro-
portion of volatile components (added as FeF3 and H20).
In the absence of calculated values f o r f HF, f F:, and f H20,
glass) also correlates with proportion of volatiles and, more-
over, for given melt compositions, increases markedly with
D increase in HEO/FeF3, consistent with the present survey of
that polymerization and temperature also exert independent
control on D(REE:FAp/melt), and the total variation in
i
D(REE:apatite/melt) in Fig. 8 can be attributed to their
combined effects (Watson and Green, 1981); e.g., the in-
crease in D (REE:FAp/melt ) for tholeiitic andesite and gran-
ite starting materials also corresponds to decrease in temper-
ature. For partitioning of REEs between immiscible silicate
liquids, D(REE) does exhibit a marked inverse correlation
with temperature (Ellison and Hess, 1989), but here the
decrease in D(REE) with increase in temperature is clearly
 Partitioning of REEs in apatite and melt 4755

l I I

40 +
/El
/
/
/
/
/
30 /
Sm///
//
/
20 / _ granite ~ X
o hawaiite, + // +
basanite [] //-- []

+ //andesite ~-o

t7
La

0 tholeiitic andesite

0 50 100 150 200

H20/FeF3
Fig. 8. Experimental results of Watson and Green ( 1981 ) for partitioning of REEs between fluorapatite and silicate
melts of varying polymerization (tholeiitic andesite and basanite to granite starting materials), temperature (950-
11200C), and pressure (0.75-2.0 GPa) compared with bulk (i.e., starting) H20/FeF3 ratio, revealing dependence on
volatile components: circles are La, pluses are Sin, squares are Dy, crosses are Lu; trend lines for La and Sm have
been fitted visually. Note that polymerization and temperature also exert independent control on D(REE:FAp/melt),
and the increase in D(REE:FAp/melt) for tholeiitic andesite and granite starting materials also corresponds to decrease
in temperature.

related to the change in composition associated with closure
of the miscibility gap.
In summary, there is ambiguity in the interpretation of the
results of Watson and Green ( 1981 ), and further experimen-
tal investigation is required to estimate the relative impor-
tance of the proportion of volatiles, melt polymerization, and
temperature on REE uptake by apatite in igneous rocks.
Acknowledgments We thank two unnamed reviewers for helpful
comments, T. Bonli for assistance with EPMA, and the Natural
Sciences and Engineering Research Council of Canada for financial
support. YP also thanks C. Holmden for stimulating discussions on
biogenic apatites.
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 Partitioning o f REEs in apatite and melt 4757

t'N
~Z

~o~o ,d

0
~Z
t'-I

t",l
~Z o5 0
e-i
o.
,6

~0
o5 o5
C~ hel
iq. ¢q
e~
0

~ . ~m~
~ 0 0 ~ 0 0 ~
m ~

eq
o~
~001~

¢~10 eq ~ 0 0 ~ 0 0 ~

05
O~
~ 0 0 ~ 0 0 ~

°~ . . . .
¢ " - 1 0 e,I ~ 0 0 ~ 0 0 ~

~ 0 0 ~ 0 0 ~

~.~ . . ~ ~.

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4758 M.E. Fleet and Y. Pan

~ qqq~
d d o o ~
. . . . . ~o . ~

~ 1 ~- I~-~

oj
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~ -= o
.= 0

&-
0
oj
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 Partitioning of REEs in apatite and melt 4759

<,-,
. . . . ~.~.~.

o o o o e
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6 6 6 ~

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o~ e

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0%. . . . 00. ~ 0. % .

o.
~m
p,.
~...~. ~.'n..
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0 0 0% r'-,'~O
4760 M.E. Fleet and Y. Pan

Appendix. Electron-microprobe results of fluorapatite (series E).

Run AP81 AP82 AP84 AP85 AP86 AP87 AP88

Analyses (12) (11) (12) (11) (11) (10) (11)
P205 (wt%) 42.2 (0.56) 41.7 (0.78) 41.8 (0.37) 41.5 (0.43) 41.5 (0.76) 41.9 (0.60) 41.8 (0.49)
SiO2 0.02 (0.01) 0.02 (0.01) 0.01 (0.01) 0.04 (0.02) 0.02 (0.01) 0.01 (0.01) 0.01 (0.01)
CaO 55.6 (0.78) 55.0 (0.59) 55.2 (0.64) 55.1 (0.83) 54.9 (0,81) 55.7 (0.51) 55.6 (0.70)
Na20 0.05 (0.02) 0.06 (0.02) 0.05 (0.03) 0.05 (0.02) 0.05 (0.02) 0.04 (0.02) 0.05 (0.02)
La203 0.10 (0.02)
Ce203 0.16 (0.02)
Nd203 O. 19 (0.03)
Sm203 0.16 (0.02)
EuzO3 0.13 (0,02)
Gd203 0.17 (0.04)
Er203 0.10 (0.02)
F 3.19 (0.11) 3.09 (0.29) 3.15 (0.12) 3.08 (0.10) 3.19 (0.09) 3.20 (0.10) 3.26 (0.10)
O --- F 1.34 1.30 1.33 1.30 1.34 1.35 1.37
Total 99.8 98.7 99.1 98.7 98.5 99.7 99.5
P 2.991 2.988 2.986 2.976 2.983 2.975 2.974
Si 0.002 0.002 0.001 0.003 0.002 0.001 0.001
Y, 2.993 2.990 2.987 2.979 2.985 2.976 2.975
Ca 4.996 4.995 4.999 5.005 5.003 5.013 5.014
RE 0.003 0.005 0.006 0.005 0.004 0.005 0.003
Na 0.008 0.010 0.008 0.008 0.008 0.007 0.008
Y~ 5.007 5.010 5.013 5.018 5.015 5.025 5.025
F 0.845 0.827 0.841 0.825 0.857 0.849 0.867
OH** 0.183 0.210 0.201 0.244 0.194 0.224 0.219
O 11.972 11.963 11.958 11.931 11.949 11.927 11.914

wt%, weight percent; *, number in parenthesis is standard deviation; chemical formula calculated on the basis of total cations = 8; **, OH
calculated based on charge balance constraint.