Geochimicn

ct Cosrnochirnica

Pergamon 0016-7037(9-4)00052-2

Acta, Vel. 58, No. ! i, op. 249.5~2.507, J994 Copyright (f:) 1994, Elsevier Science Ltd Printed in the U3/\._·;_AIJ rights reserved 0016·7037/94 %.00 + .00

Uranium in granitic magmas: Part 1. Experimental determination of uranium solubility and fluid-melt partition coefficients in the uranium oxide-haplogranite-H20-Na2C03 system at 720-770°C, 2 kbar
CHANTAL PEIFFERT, MICHEL CUNEY, and CHINH NGUYEN-TRUNG Centre de Recherche sur la Geologie des Matieres Premieres Minerales et Energetiques and GdR CNRS-CREGU 0077, BP 23,54501 Vandoeuvre les Nancy, Cedex, France (Received March 17, 1993; accepted in revised form Januarv 18, 1994) Abstract-The solubility of uranium was investigated in both carbonated aqueous fluid and granitic melt in equilibrium in the system haplogranite-uranium oxide-H20-Na2C03 (0.5-1 molal) at 720-nO°C, 2 kbar, and fo, fixed by Ni-NiO, Fe304-Fe203, and Cu20-CuO buffers. As complete solid solution exists between U02.00 and ·U02.25 (i.e., 75 mol% UOz + 25 mol% U03), three distinct uranium oxides: UO(2c01±O.OI), U0(2.W±0.02J, and UO(2.Z5±002)were, respectively, obtained at equilibrium, under the three fo, conditions cited above. Thus, the percentage of U (VI) in uranium oxide increased with increasing log fo,. The thermal decomposition of Na2C03 to CO2 and Na-O led to the decrease of the sodium carbonate concentration from 0.5-1 molal to ~ 10 -2 molal in all aqueous fluids and to the dissolution ofNa in the silicate melts. Crystal-free silicate glasses with four agpaitic coefficients, ex = ((Na + K)/ AI) = 1.1, 1.3, 1.5, and L 7 were obtained. The uranium solubility in 10-2 m aqueous carbonated fluid (( 8.1 ± 0.1 ) :s: quench pH :s: (8.9 ± 0.1» was in the range 1-[ 7 ppm and increased linearly with increasing /0, according to the expression: log (U) (ppm)
= 0.09 . log fo, (bar)

+

1.47.

This equation is valid for the temperature range 720-nO°C and 2 kbar. U (IV) carbonate possibly were major species in aqueous solutions under reducing conditions (NiNiO buffer) whereas U(VI) carbonate complexes dominated under higher oxidation conditions (Fe304Fe203, CUzO-CuO buffers). =-= The uranium content in silicate glasses varied in a large range (102:"2';>< 105 ppm) and log (U) (ppm) increases linearly with both fo, and ex in the range 1.1-1.5 according to the equation log (U) (ppm) = 0.04 log fo, (bar)

+ 3.80ex

- 1.34.

This equation is valid for (I) foz ranging from Ni-NiO to CU20-CUO, and (2) the temperature range 720-nO°C at 2 kbar ..The effect of fo, on the uranium solubility in silicate melt slightly decreased with increasing a from 1.1 to 1.5. For a in the range 1.5-1.7, the effect of both fo, and agpaicity index on the uranium solubility was considerably reduced. The temperature variation in the range 72o-noDe had no significant effect on the uranium solubility in either aqueous liuid or silicate melt. The partition coefficient (Dfluid/melt) of uranium was in the range 10-40_10-15 and depended on both fo, and ex according to the equation log
Dfluid/melt

=

0.05 log f02 (bar) - 3.78a

+ 2.84.

The validity conditions of this equation are similar to those of the preceding one. Results obtained. in the present study could be used to predict the geochemical behaviour of uranium during magma fra-ctionation and to further understanding of the formation of uranium ore deposits related to partial melting or fractional crystallization of felsic magmas. The genesis of the Kvanefjeld (Ilimaussaq, Greenland) uranium deposit is discussed. INTRODucnON PARTIAL MELTING AND crystal fractionation represent the most powerful processes leading to a steady enrichment of lithophile elements such as uranium in the Earth's lithosphere and more particularly in the upper part of the continental crust (ROGERS and ADAMS, 19:69; TAYLOR and McLENNAN, 1985). Although uranium can be strongly partitioned in a large variety of early crystallizing minerals in granitic magmas such as zircon, apatite, monazite, titanite, uraninite, and ur2495

anothorite (CUNEY and FRIEDRICH, 1987), the most felsic members of granitic associations are generally enriched in uranium. Thus, measuring uranium solubility as a function of composition of silicate melt may allow us to predict uranium concentration trends in magmas as they differentiate. The determination of fluid-melt partition coefficients of uranium is fundamental for the prediction of uranium concentration in fluids coexisting with granitic magmas. The knowledge of uranium solubility and fluid-melt partition coefficients is of major importance for the understanding of the distri-

2496 bution processes. of the major heat authors producing deposits have

e. Peiffert, M. Cuney, and e. Nguyen-Trung elements resulting carried out in the -Earth from magmatic experimental in waterdissolution ( 1150FARGES and ANet 1985) is much higher than that of U (IV). In the present study, the· equilibrium was attained using three approaches: I) normal experiments using U (IV) oxide as starting materials 2) reversal experiments using dissolved or solid U (VI) specie; as starti ng materials, and 3) experiments using a system undersaturated with uranium. At equilibrium, all the three above-mentioned types of experiments having the same fluid-melt composition, under identical P, T, fo conditions, should provide similar partition coefficient (Dflmd/melt) of uranium. Moreover, both normal and reversal experiments should give the same results regarding ( I) the uranium oxide composition and (2) the uranium solubility in aqueous fluid and silicate melt. ' Starting materials used in normal experiments were ( I)stoichiometric sintered spheres of U02.000 (~IOO J.lm in diameter). U02000 were obtained by reduction of natural U02.I'O by a Ti-Zr mixture in vacuum at 900°C during 36 h. U)OS and U02(OHh· H20 were also used in reversal experiments; (2) Na,C03 solutions (0.5, 0.8, and 1.0 molal) (Analytical Reagent); (3) dehydrated synthetic gels with four compositions, indicated in Table 1. were made using the method of HAMILToN and HENDERSON (1968). Chemicals used were certified Na2C03, K2C03, AI(NO))· 9H20, and (C,Hs)4Si04 (Analytical Reagents). For several reversal experiments, three different starting materials were used: (I) Na,CO) solution oversaturated with uranyl (VI) and gel, (2) Na,CO) solution and gel doped with uranium as U )Og (0.5-2 wto/c), and (3) Na,CO) solution, gel, and schoepite UO,(OH),· H,O. For normal experiments, samples were prepared using a quadruple capsule technique. About SO rng of stoichiometric U02.000 and about 200 mg of gel were loaded into separate platinum capsules (3.6 mm ID, 4.0 mm OD, 8.0 mrn long for UO" and 25.0 mrn long for gel). These two platinum capsules were only crimped. About 100 mg of one of the three assemblages (Ni-NiO, Fe)04-Fe,O), or Cu,O-CuO) and 100 mg ofH,O were loaded in the third platinum capsule (3.6 mm ID, 4.0 mrn OD, 25.0 mm long). This capsule was welded shut. The three platinum capsules containing U02, gel, and oxygen buffer along with about 200 mg of Na2CO) solution were loaded into a gold capsule (5.0 mm ID, 5.8 mm OD, 65.0 mm long). The gold capsule assembly was welded shut and loaded in a cold-seal pressure vessel. The end containing the UO, capsule was placed in the bottom, i.e., the warmest part of the vessel. The capsule with the gel was placed adjacent to the UO, capsule (Fig. I). This technique has two major advantages: (I) UO" loaded in excess, represents an inexhaustible source of uranium and thus saturates the system with this element; and (2) the separation ofUO, and gel before the experiments prevents UO, particles from entering the silicate melt and aqueous solution, thus preserving pure solid and aqueous phases after the run. Chemical reactions between UO, and silicate melt only occur through aqueous carbonated solutions. For reversal experiments, the triple capsule technique was used to prepare samples. Two platinum capsules containing gel doped or not with U (VI) and oxygen buffer along with about 200 mg of Na,CO) solution free or oversaturated with uranium were loaded into a gold capsule. The dimensions of platinum and gold capsules are similar to those cited above. Pre-run rupture tests of platinum and gold welded capsules were systematically done by placing them overnight in an oven at l20°e. Subsequent weighing checked for possible leaks. Experimental Procedure

and the genesis

of uranium

Several

studies using two approaches. In the first approach, experiments free systems in synthetic 1600°C) and et al., 1992; aI., 1981, from melt these under to study silicate the mechanisms melts pressure 1980,

were conducted of uranium temperature 1979; SCHREIBER Results dissolved (CALAS,

at very high 1983;

atmospheric SCHREIBER,

DREWS, 1980; SCHRElBER works three indicated valence depend
0:

and BALAZS, 1982; SCHREIBER obtained that states-IV, uranium

1982; DOMINE and VELDE, 1985).

in the that melt melt auwt%
0'

V, and

VI-and

the proportions agpaitic and thors

on the imposed

coefficient

= (Na

+ K)/
and

f02. The effect of the

Al of aluminosilicate in alurninosilicate VELDE ( 1985). solubility with These (41.8-67.5 increasing

fa, on the uranium
have shown

solubility

was determined

by DOMINE

that the uranium increased

U30S> in aluminosilicate fo, at 1400°C, I bar.
In the
(Dflu;d/melt)

and

second silicate cases, and

approach, were and buffer, melt

fluid-melt determined aqueous

partition
between solutions

coefficients synthetic 2 conditions. silicate of Hel CO2, HF 1991), at 750°C,

of uranium a Ni-NiO starting

or-ruitural kbar, melt under and In most (KEPPLER (ZHARIKOV (Na, K)CI,

close to geological with variable

materials

used were synthetic amounts

aqueous

solutions

WYLLIE, 1990, 1991), H20 et al., 1987; KEpPLER and WYLLIE, K)F, Other Ag2C204 (ZHARIKOV experiments et a!. ( 1989) zircon were done are difficult which and H20

+

1990,

(Na,

et aI., 1987;

Yu-

DINTSEV, 1990). topaz-rhyolite obtained because nificant to 4 kbar

using natural Results sigof 2 from (0.78 to consider The effect

melt and NaCI (WEBSTER et a!., 1989). contain incorporates pressure

by WEBSTER final glasses amounts on the

of uranium uranium

in its structure. solubility

temperature

in the range

750-1000°C

s; 0: = (N a + K) / Al s; 1.08) containing by ZHARIKOV et a!. (1987). However, uranium state reported from because and, above-mentioned in some cases, used with caution of the system of the composition to fluid-melt This paper

in haplogranite

D fluid

was measured Zmelt values of must be

studies

of lack of data on the equilibrium on the modification fluid after a run, due dealing and aqueous

of melt

interactions. is the first of a series determination partition solution, and aqueous silicate coefficient of contributions
(Dflu;d/melt)

with the systematic and the fluid-melt between ligands perature, reports haplogranite in aqueous and

of the urani urn solubility

of uranium
of tem-

solution

as a function

melt composition,

been reported

(PEIFFERT

fo, at equilibrium. Preliminary results have et al., 1992), and the present study
data concerning
0'

comprehensive range

the system

uranium

oxide-haplogranite
temperature fixed by three buffers:

(1.1 s;
720-770°C, Ni-NiO,

s; 1.7)-H20-Na2C03 in the 2 kbar, under fo, conditions Fe304-Fe203, and Cu20-CuO.

EXPERIMENTAL Starting Materials and Preparation of Samples

Earlier works have reported that the solubility of U (VI)' in aqueous fluid (RED'KIN et al., 1989) and silicate melt (DOMINE and VELDE,

Most experiments (80%) were conducted with a rapid-quench coldseal pressure vessel similar in design to that used by FRANTZ and Por= (1979). All other runs were done in conventional cold-seal pressure vessels. The reaction vessel was externally heated in a horizontal electrical furnace. Experiments were done at 2.00 ± 0.0 I kbar and two temperatures: 720 ± 15 and 770 ± 15"C. A mixture of water and soluble oil was used as a pressure medium. Total pressure was measured using a Heise gauge and temperature with calibrated chromel-alumel thermocouple. The temperature gradient in the vessel at 2 kbar in tbe temperature range nO-770°C was determined using two internal chromel-alumel

2497 Trace amounts of dissolved uranium were determined bv visible absorption spectrophotometry using Bromo-PADAP as chromogenic reagent with a relative uncertainty within 10%. The detection limit is 20 ng of uranium. Several runs were made to determine whether dissolved uranium precipitated during the quenching. Two techniques were used. The first technique employed The same starting materials and the loading system as in normal experiments. After each run, the gold capsule was punctured, the aqueous fluid was extracted and the platinum capsule containing uranium oxide was carefullv removed Then the two platinum capsules containing silicate glasses ;nd oxyge~ bufle; and the gold capsule were boiled in I m HCl to dissolve possible uranium precipitates. The total uranium content determined in the filtered solid and in 1 m HCI obtained after boiling the capsules was always below 10% of the uranium content measured in the filtered solution. In some experiments, total uranium was also analysed in non filtered aqueous fluid mixed with the above cited 1 m HCI solvent. Results of this measurement agree fairly well with those obtained from filtered aqueous fluids. The difference between the two sets of results was below 10%. In the second technique, an additional platinum capsule (3.6 rnrn ID, 4.0 rnrn OD, 20.0 mrn long) perforated with many holes less than 0.2 mrn diameter and loaded with purified quartz grains approximately 10}1m size was placed in a gold capsule with three other reduced size platinum capsules containing U02, silicate glass, and buffer. On quenching, the aqueous fluid was trapped in interstices ofquartz grains inside the perforated platinum capsule. The perforated , platinum capsule was extracted ffflrrfthe gold capsule and was rapidly weighed. The capsule was then dried in an oven at 110°C overnight. This drying condition was adopted since experiments at temperature up to 200°C indicated that water extraction from quartz grains was total after 2 h at 110°C. After drying, the capsule was reweighed. The difference is the weight of the aqueous fluid. The platinum capsule was then carefully opened. Both quartz grains and the platinum capsule were hoi led in I m HNO] and the analysis or this acid solution provides the total uranium in the aqueous fluid. In the last technique, the amount of uranium is up to !0% higher than that determined in filtered solutions (Table 3). The uranium excess determined in this case is in the same order of magnitude as the measurement uncertainties. For this reason, the precipitation of uranium during quench: ing is considered negligible, and the amount of uranium measured at ambient conditions represents effectively the uranium solubility in aqueous fluid at high P, T conditions. The molalities of Na, K, and Si were determined by atomic absorption spectrometry (relative uncertainty = 5%). Trace amounts of aluminium were below the detection limit (30 ppb ) of atomic absorption spectrometry. Total aqueous carbonate was determined by ion chromatography (detection limit: 0.1 ppm). Analysis of oxygen buffers, uranium oxides, and silicate glasses

Au
Capsul

U02

e

_W---

Na2C03 SOLUTION

GEL

Pt
Capsules

FIG. I. The quadruple partitioning experiments.

capsule (1 Au, 3 Pt) used for the fluid-melt

thermocouples with their ends located 2S mrn from each other. In order to duplicate the actual run conditions as closely as possible, the couple was successively inserted in ( I ) a Ni filler rod (80 mm long) which was ~d along its axis to allow the thermocouple to pass through and (2) a dummy charge gold capsule (30 mrn long). The latter was placed at the tip of the thermocouple. Results obtained indicated a gradient ~f 2eC for each 10 mm. The telr~ature gradient for a gold capsule 6) rnrn long was estimated to be 14°C across the charge. Run durations were in the range 2-4 weeks. At the end of each run, the rapid-quench cold-seal pressure vessel was tipped and brought to a vertical position so that the capsule slid from the hot end to the cold end of the vessel under constant pressure (2 kbar). Estimated quenching time was 5 sec. This value was close to the quenching time (4 sec) of a similar gold capsule (70 mrn long) containing three empty small platinum capsules UD mrn long) heated to no°c, I bar, and plunged into H20 at ambient conditions. The conventional cold-seal pressurized vessel was disconnected from the pressure line and was withdrawn from the furnace. Pressurized air and water were used to quench the vessel. 3 minutes were necessary to bring back the vessel to room temperature and approximately 50 bar. Analysis of run products yielded similar results for both types of vessel. Analysis After Aqueous Uranium from the Analysis of Run Products and Uncertainties Evaluation

removal from the vessel, the gold capsule was opened. solution was removed using polyethylene transfer pipets. oxide, silicate glass, and buffer assemblage were extracted three platinum capsules. ofaqueous fluids

The buffers were checked by X-ray diflractometry to determine whether any of the phases had been exhausted during the run. It is well known that a complete solid solution exists between U0200 and U0225 (i.e., 75 mol% UO, + 25 mol% (03). The composition of the solid solution UO(2+X) after each normal experiment was determined as follows: X-ray diffractometry was first employed to determ ine the u nit cell parameter a., (A) from the position of the (620) band of cubic UO(2+x)(0 50 X 50 0.25). Values of a.; (A) obtained were then used to calculate the fraction x ofUO, in the solid solution UO(2+x) based on the linear correlation between a., (A) and x (0.00 50 X s: 0.25) (CATHELINEAU et al., 1982) according to the Eqn. I: ao(A)
= -0.116x+

5.471.

(I)

Quench pH was rapidly measured (uncertainty ±0.1 pH unit) at room temperature using a microcombination glass pH probe (Mi .. croelcctrodes MI-410). The aqueous sample was then rapidly and carefully filtered using an ultrafiltration membrane (Millipore PTGC, diameter! 3 mm). The filtered solid consists of silicate glasses and trace amounts of uranium and aluminium. The filtration of aqueous solution was necessary to prevent all risks of accidental presence of uranium oxide particles from U-bearing capsule.

For reversal experiments, the amount of uranium oxide precipitation obtained after each run was not sufficient to be analysed with accuracy. Careful observations of run products using polarizing microscope, electron microprobe, and scanning electron microscope diclnot reveal the presence of any additional solid compound containing uranium and silicate glass constituents (AI, Si, Na, K) after the run. Five elements, Si, AI, Na, K, and U of silicate glasses were analysed by electron microprobe (Cameca SX SO). Low uranium concentra-

2498

C. Peiffcrt, I\1. Cuney, and C:. N~~uYf:'n-Tn!ng
5

tions were calibrated against a NBS standard (:161.5 ppm). The determination of four major elements was done at the acceleration voltage of 15 KeY, enlarged analytical spot (diameter = 20 itm), low beam-current ( 10 nA), and a short integration period (105) in order to ininrmize alkali loss. Uranium was analysed with a beam current in the range 30-60 nA and a relative long integration period (30-60 sec). The detection limit for uranium was 120 ppm. For glass samples containing uranium less than 1000 ppm, both electron microprobe and fission track methods were used to analyse the uranium content. The measurement technique for the latter is as follows: fission tracks of235U fragments, from irradiation by thermal neutrons, are recorded on a thin kapton film (thickness = 0.5 mm) placed upon the polished surface of the sample. Submicroscopic fission tracks on kapton are enlarged etching in a NaCI, NaCIO solution. The uranium concentration is determined by comparison of the number of revealed fission tracks per surface-area unit of the kapton between the sample and NBS glass standards. Electron microprobe and fission track methods yielded similar results within 7% for low uranium content ( -ISO ppm) and 4% for uranium concentration in the range 340-540 ppm. In order to check the homogeneity of the silicate glass and its uranium content, three glass chips were taken at about 5, 10, and 20 mm from the U-bearing capsule (see Fig. I) and were systematically analysed. Spot analyses were done from one edge to the another through the center of eachsample. Results indicated that, within a given glass sample, concentrations of Si, AI, Na, K, and U fluctuated within 3%, but this fluctuation appeared to be random. For uranium, a small concentration gradient up to 3% was observed between the sample located at 5 mm and two other samples at 10 and 20 mm from the U-bearing capsule. This concentration gradient, valid for the large a range 1.1-1.7, was at most in the same order as measurements relative uncertainties for uranium (3-6%) and was thus considered as negligible in the present work. For four runs, Na and K contents in glass were determined by both electron microprobe on glass samples and global analysis of glass using atomic absorption spectrometry. The good agreement within 4% between results obtained from two methods (Table 2) attested the reliability and the accuracy of analysis by electron microprobe. Total H20 content in silicate glass was estimated as the complement to 100 wt% of the electron microprobe analysis. For four runs, total H20 content was determined using the Karl Fischer method. The principle of the method is as follows: (1) water vapor from the heated glass sample (1250°C) is collected in a titration cell; (2) H,O is then titrated potentiometrically according to the redox reaction: (2) The agreement between these two methods was within 10%. Total dissolved CO, in silicate glass was determined using pulse coulometry. Total CO2 gas, extracted from a glass sample at IIOO°C, is transported by a neutral gas to a titration cell and reacts with Ba(CIO.h solution at pH = 9. The pH modification resulted from

T

i
I
(b)

S P-<
;:J

3

'1

:______;~
Q~

a=~ a=1.5 a=1.3

m
Fi (r T

a=1.l sc

3<

2

~

.s

eo

a
\\

v

o

(a)

s

F c
1

-1 +---~_---.----~---.----_----.----.-_ __~ -20 -10 -5 -15 o

log £02 (bar) FIG. 3. (a) Correlation between uranium solubility (U (ppm)) in carbonated fluid and log fo, (bar). (b) Correlation between uranium solubility (U (ppm)) in silicate granitic melt and log fo, for agpaitic coefficient a = 1.1, 1.3,1.5,1.7. (square: Ni-NiO; circle: Fe30.-Fe203; triangle: Cu20-CuO; +Reversal experiments).

the precipitation of BaC03 is determined detection limit is 50 ppm of CO2• RESULTS Table Weight displayed electron

by pulse coulometry.

The

2

shows

analytical of metal

results oxide~etal

obtained
= U,

in silicate

melt.

percent

in Table microprobe

2 represent
measurements

mean

Na, K, AI, Si) values of numerous
range.

and its variation

The chemical composition of aqueous fluid after a run as well as the partition coefficient (D fluid/meil) of uranium are reported in Table

3.
of the System
of uranium three

Equilibrium
The have

Conditions

dissolution been measured Results (Fig.

kinetics under obtained

/0,

in the silicate conditions that a minimum

melt run into ad-

fixed in the to attain took

experiments. duration equilibrium account ditional

indicated

of two weeks only experiments conditions: solubility melt repeated

was necessary which

for the system study

2). Moreover,

the present

fulfill the four following

40000

I[:, o

Cu20·CuO NI-NiO

F~304-F,e203

'I

I) Uranium
and have 2) The must silicate been

measurements must

in both

aqueous

fluid

a
:::>

ro

III III

30000
[:,

o

All experiments at least three times (Tables 2 and 3;
be reproducible. uranium tracks in silicate glasses concenresults by electron from or very the

Fig. 3). distribution of dissolved of fission points in both be homogeneous. below This characteristic was controlled analytical

20000

[:,~rf--I:>--6

0. 0.

E

10000

~g
~D

0

(")

by the distribution trations obtained on various solubility and reversal

for uranium

1000 ppm and by similar concentrations.

of the ~ame sample

0

microprobe 0 10 20 30 40 3) Uranium normal 4) The same

for higher

fluid and melt obtained must after be similar

Duration (days)
FIG. 2. Kinetics of uranium dissolution in silicate glass in the system uranium oxide-haplogranite-H20-Na2C03 at nO-770°C and 2 kbar.

experiments obtained must

close together uranium redox

(Tables oxides condition

2 and 3; Fig. 3). the runs under have the same composition.

Partitioning. of U between granite melt and aqueous fluids These conditions are considered as four reliable experimental proofs indicating that the system is in equilibrium. Figures 3, 5, and 6 display only values obtained at equilibrium (run duration 2 15 days). The Composition of Uranium Oxides
Table 1. Composition

2499
materials (aqueous solutions and gels)

<?! starting

gel compositions
wt%

G1 82,5 13,1

G2 78,4 12,5 4,2 4,9 52 0.8m

G3 80,0 12,8 4,3 3,0 53 0.5m

G4 76,9 12,3 4,1 6,9

Results obtained from quantitative analysis of uranium solid phases using X-ray diffraction patterns indicated that only well-crystallized cubic uranium oxides in equilibrium with fluid and melt were formed after each run. The three values of cell parameters a., determined were: (5.470 ± 0.02), (5.459 ± 0.02), and (5.442 ± 0.02) A corresponding, respectively, to the three f02 values fixed by the Ni-NiO; Fe304Fe203 and Cu20-CuO buffers (Fig. 4). The plot of the values of a; (A) in the linear Eqn, I led to three compositions: UO(2.01±O.OI); O(2.10±O.02); nd UO(2.25±O.02)' igure 4 shows U a F that two phases U02.01 and U0210 obtained under reduced conditions (Ni-NiO and Fe304-Fe203) agree fairly well with U02.DO and U02.00 + U409 predicted by calculation using thermodynamic data (GReiNvOLD et aI., 1970; MAGLIC and HERAK, 1970; FUGER, 1971; MACLEOD, 1972; ROBIE et aI., 1979). On the other hand, a r.l.issrepancy between experimental measurements and theoretical prediction was observed at the most oxidizing conditions. Under f02 fixed by the Cu20-CuO buffer, cubic U02.2S is precipitated whereas calculations predicted the formation of orthorhombic U 308' The Composition of Aqueous Fluids

5,02 AI203 K20 Na20 starting solutions Na2C03 (moll kg H2O)

4A
0,0 51 1m

54
0.1 m

surface of silicate glass, revealed scope. No U-Si solid compound The uranium concentration fluid varied in the range 1-17 concentration increased linearly '3; Fig. 3a): log (U) (ppm)
=

by scanning electron microwas observed. in the carbonated aqueous ppm. The logarithm of its with increasing log f02 (Table

0.09·log

f02

(bar)

+

1.47.

(4)

Variations of the silicate glass composition and the temperature in the range 720-770°C appear to have no significant effect on the uranium solubility in the carbonated aqueous fluid. Characteristics and Composition of Silicate Glasses

After the experiment, the sodium carbonate concentration decreased from 0.5-1 molal to 10-2 molal in all aqueous fluids, resulting from the thermal decomposition ofNa2C03: Na2C03 (aqueous)
= Na20 (melt)

+

CO2 (gas).

(3)

Na20 enters the silicate melt by affinity. The transformation of a major part of the carbonate to carbon dioxide decreased the pH of the solution from the initial value (12.1 ± 0.1) to quench values in the range 8.1-8.9. The potassium concentration was in the range 113-153 ppm. The solubility of aluminum could be estimated as lower than 30 ppb. Si02 concentrations, determined in some runs, were in the range 600-1000 ppm. These low values resulted from precipitation, during quenching, of pure Si02 on the

O,3.---------------~

0,2

o
0,1
/::. Cu20.cuO

0,0 L - 20

-~-a-~--r-:;::::=:;::=====- 15 -10 ·5

o o

Fe304-Fe203 Ni·NiO

o

log £02 (bar)

FIG. 4. Correlation between x of uranium oxide (UO(2+x)) and log fo, (bar).

Yellow color and strong UV fluorescence characterized glasses at equilibrium under Fe304-Fe203 and Cu20-CuO buffers. Under the Ni-NiO buffer, the glasses were colorless. Numerous two phase (aqueous carbonated solution, vapour) and some three phase (solid, aqueous carbonated solution, vapour) fluid inclusions, between 5 and 80 /-Lm size, were trapped inside silicate glasses, probably during the quenching. The distribution density of the inclusions has been estimated from scanning electron microscope images. However, fluid inclusions represented only 0.2 wt% H20, whereas water content was up to 13 wt% of total composition of silicate glasses (see results below). Silicate glasses with agpaitic coefficients a between 1.1 and 1.7 were obtained by varying the amount of Na20 in the starting gel and the concentration of Na2C03 in the starting solution (Tables 1 and 2). An increase of the sodium content in all silicate glasses compared to the starting gel compositions resulted from the incorporation in the melt of Na.O produced from the thermal decomposition ofNa2C03 as discussed previously. Relative concentrations of other major constituents (Si, AI, K) of glasses remain practically unchanged. H20 contents in silicate glasses measured by the Karl Fischer method were found to be 10.15, 11.98, and 9.10 w1% with relative uncertainty ± 0.05 wt% in runs 2-5, 2-24, and 3-18, respectively. These values are similar to the H20 contents estimated from the complement to 100 wt% of the electron microprobe analysis (respectively: 10.62, 11.92, 9.18 wt%; Table 2). A concentration of 0.11 ± 0.01 wt% CO2 was obtained for a = 1.5 (runs 2-5 and 2-24). This value appears to be independant of f02• Uranium contents of silicate melts varied in a large range 1.43 X 102-3.37 X 105 ppm U. Increasing a from 1.1 to I.S and increasing f02 values led to a linear increase of uranium solubility in the silicate melt of several orders of magnitude (Table 2: Fig. 3b). However, the effect of fo, on the uranium

~_~~. ~~,_"'~: ,~-~.~-.-._~ .. __ .. ..... ...._:~~~.:~>'"':"~-~_=-::~~c~--..~ _, ..~- .._.'._ ~

_

."~

•. -4"'-'_ • ."

_._~~.~.

...

.--.-===~::;::'2_E~:~_.;=~·.~=~~-----,
-_
<' _.

2500
Table
Run 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-11 2-12 2-13 2-14 2-15 2-16 2-17 2-18 2-19 2-20 2-21 2-22 2-23 2-24 2-25 2-26 2-27 2-28 2-29 2-30 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 3-10 3-11 3-12 3-13
3-14

C. Peiffert, M. Cuney, and C. Nguyen-Trung 2 . Chemical
days nb. CA.
R.Q. R.Q. R.Q.

composition
Nature

of silicate
T
(0C)

glass
Si02
wt%

after run.
A 1203
wt%

gel

log [02
(bar)

K20
wt%

Na20
wt%

U02
\vt%

H20
wt%

K/(Na+K)

(Na+K)/

AI

G+s G4+S2 idem idem idem idem idem idem
idem

mg
180 175 195 185 177 169 189 199 156 214 163 163 182 196 179 196 188 177 164 199 195 187 188 168 169 153 156 174 199 194 195 197 183 188 178 196 199 197 261 155 178 166 156 142 123 145 136 133 122 133 152 123 144 175 164

15 15 21 15 15 21 15 15 21
us

720 770 770 770 770 720 770 770 770 770 720 770 770 720

-15.6 -15.0 -15.0 -103 -10.3 -10.9 -4.0 -4.0 -4.0 -15.0 -15.6 -15.0 -15.0 -lS.6 -15.6 -15.6 -15.6 -J5.6 -10.3 -10.9 -10.3 -10.9 -10.9 -10.3 -10.9 -10.9 -10.9 -10.9 -4.0 -43 -4.3 -4.3 -4.3 -4.0 -4.3 -4.3 -4.3 -4.3 -4.3 -4.0 -15.0 -15.6 -15.0 -15.0 -15.6 -lS.0 -15.0 -10.9 -10.3 -10.3 -10.3 -10.9 -10.3 -10.3 -4.0 -4.3

62.410.2 62.5±0.3 62.5±0.2 61.910.4 61.4±0.3 62.3±0.3 61.7±0.4 6T.7±0.4 61.S±0.2 68.1±0.3 67.0±0.2 67.4±0.2 67.9±0.3 68.2iO.4 67.4±0.2 68.4±0.4 63.9iO.4 63.9iO.2 65.S±OJ 64.6±0.3 68.4±0.2 68.2iO.2 65.0±0.3 68.3±0.4 68.5±0.3 67.9±0.4 64.310.4 64.2SiO.3 643±0.3 64.9±0.5 64.15±O.2 65.2±0.2 64.7±0.4 63.9±0.3 63.9iO.3 64.1±0.3 64.2iO.3 64.2iO.3 69.5±0.3 69.4±0.3 69.1±0.3 69.4±0.4 69.3±0.4 69.1±0.4 69.3iO.S 69.JiO.4 69.3±0.3 69.45±0.3 69.5±0.3 69.4±0.3 69.3±0.2 69.610.3 67.5iO.3 70.6±0.3 69.3±0.2

10.2±0.1 10.2±0.2 10.O±O.2 10.1±0.2 10.4±0.1 10.2±0.1 10.1±0.2 10.2±0.2 10.2±0.2 1O.0±0.1 10.7±0.1 10.5±0.1 10.8±0.1 10.4iO.2 10.3±0.1 10.6±0.1 10.SiO.J nOiO.l 10.5±0.1 10.8±0.1 10.3±0.1 10.SiO.l 10.4±0.1 l1.1±0.1 10.910.1 10.8±0.1 1O.8iO.l 11.0iO 1 10.7±0.1 10.4±0.1 10.3±1I.1 105±1I.1 11135±0.1 10.9±0.1 10.6iO.1 10.9±0.1 11.1iO.J 1O.8iO.l 9.2±0.1 10.6±0.1 10.5±0.1 10.4±0.1 10.65±0.1 10.7±0.1 lO.4iO.OS 10. 7iO. 1 10.410.1 10.6±0.1 10.7±0.1 10.6±0.1 10.6±0.1 lO.SiO.2 JO.9iO.l 10.9±0.1 1l.1±0.1

3.6±0.1 3.7±0.1 3.5±0.1 3.5±0.1 3.7±0.1 3.5±0.1 3.4±0.1 3.5±0.1 3.5±0.1 3.b±O.1 3.7±0.1 3.7±0.01 3.6±0.1 3.6iO.05 3.5±0.05 (3.48) 3.7±0.04 3.810.1 .l.8iO.J 3.6±0.1 3.4±0.1 3.5±0.05 (349) 3.5iO.l 3.6±0.04 3.6±0.1 3.50±0.05 3.45±0.1 3.610.1 3.810.1 3.7±0.1 3.7±0.1 3.7±0.1 3.7±0.1 35S±0.1 3.h±O.1 3.8±0.1 3.7iO.1 3.7±0.1 3.6iO.1 3.810.1 3.2±0.05 4.1±0.1 4.0±0.1 3.910.05 (3.82) 4.0±0.1 3.95±0.04 4.0310.03 3.810.1 4.0±0.1 4.0±0.1 3.9±O.OS 4.1±0.1 4.1±0.05 3.84iO.03 3.5iO.Ol 4.1±0.05 3.3±0.1

8.1± 0.1 8.1±O.1 8.0±O.1 8.2±O.1 8.3±O.1 8.3±O.1 8.0±O.1 8.3±0.1 8.3±0.1 7.9±0.1 8.0±O.1 7.8±O.1 7.2±D.l 7.310.1 7.2±D.l (7.03) 7.1tD.1 7.6iO.1 7.4iO.1 805±0.1 7.6±O.1 7.2±0.1 (7.06) 7.4SiO.1 7.4±0.1 8.3±D.1 7.6±0.05 7.6±D.l 7.4iO.l 7.7iO.1 7.2±D.l 7.6±0.1 7.2±0.1 7.l5±O.1 75±0.1 7.2±O.1 7.45±0.1 7.StO.Ol 7.6±0.1 7.7iO.1 8.0iO.1 7.6±D.l 5.8±D.1 5.7±D.1 5.6±D.1 (5.58) 5.9±0.1 5.9±0.1 5.710.1 5.8iO.OS 5.7±0.1 5.9±0.05 S.9±D.l 5.8±0.1 5.81±0.1 5.80iO.l 6.65iO.05 6.3±0.04 6.9±0.04

2.8 ±0.1 3.0±D.2 3.110.1 3.2±D.2 3.2±D.1 3.1±D.l 3.3±D.1 3.4±D.l 3.4±0.1 0.45±0.06 1.08±D.02 0.97±D.06 1.04±D.04 0.9210.04 0.97±D.06 0.98±D.05 0.9110.05 0.95iO.06 1.25±0.06 1.31 ±0.06 1.46±0.06 1.47iO.06 1.45±0.07 1.51±D.04 1.49±0.03 1.50±D.02 1.3310.05 1.5610.05 2.76±0.06 2.40±0.06 2.1O±0.06 2.19±D.07 2.19±O.06 2.23±O.04 2.21 ±D.03 2.1310.04 2.18±0.04 2.0110.04 2.4110.04 0.45±0.05 O.09b±D.Ol O.l1±O.Ol 0.12±D.01 0.12±D.01 0.12±O.01 0.0910.01 0.13tO.01 O.lb±O.01 0.15±0.01 0.16±O.01 0.155±0.01 0.16±0.01 0.14tO.Ol 0.17tO.01 0.33±O.02 0.35±0.02

12.92 12.62 12.85 13.09 12.97 12.62 13.53 13.02 12.81 9.97 9.59 9.63 9.36 9.58 10.62 9.20 13.39 J2.95 12.25 9.12 8.84 12.05 7.18 8.04 8.75 12.35 11.70 11.35 11.24 11.64 12.07 1136 11.92 11.79 12.16 10.92 11.45 10.79 10.01 9.97 10.55 10.70 10.03 10.24 10.49 10.28 10.41 9.91 9.77 9·91 10.12 10.11 11.22 7.74 9.08

0.23±0.01 0.23±0.01 O.22tO.Ol 0.22±0.01 0.23±0.01 0.22±0.01 0.22±0.01 0.22±0.01 0.22±0.01 0.23±0.01 0.24±O.01 0.24±0.01 0.25±0.01 0.24iO.01 0.24±0.01 0.26±0.01 0.25iO.Ol 0.2510.01 0.23±0.01 0.24±0.01 0.24iO.OJ 0.24±0.01 0.22±0.01 0.23±0.01 0.23±0.01 0.25iO.01 0.24iO.Ol 0.25±0.01 0.24±0.01 0.25±0.01 0.25±0.01 0.24±0.01 0.25±0.01 0.25±0.01 0.25iO.Ol 0.24±0.01 0.23iO.Ol 0.2410.01 0.22±0.01 0.32±0.01 0.32±0.01 0.3l±0.01 0.31±0.01 0.31±0.01 0.32iO.Ol 0.30iO.OJ 0.32±0.01 0.31±0.01 0.30±0.01 0.32±O.01 0.32±0.01 0.30iO.OJ 0.26iO.OJ 0.30±0.01 0.24±0.01

1.6910.05 170±0.OS 171±0.05 1.71±0.05 1.70±0.04 1.70±0.05 1.68±0.05 1.72±0.06 1.70±0.06 1.70±0.04 1.61±0.04 1.60±0.04 1,.4610.03 1.S2iO.04 1.52±0.03 1.4910.04 1.59iO.04 1.47iO.04 1.63±0.04 1.50±0.03 1.52±0.03 1.52iO.04 1.54±0.03 1.57±0.03 1.50±0.025 1.51±0.03 J.49iO.03 1.S2iO.03 1.55±0.04 1.55±0.05 1.52±0.04 1.56±0.04 1.54±0.04 1.52±0.04 1.51±0.03 1.55iO.04 1.51±0.03 J .48iO.o3 1.59iO.o4 1.5910.05 132±0.034 131±0.03 1.2910.03 J.32±0.033 1.30±0.03 1.32iO.oZ 1.27iO.o2 1.32±0.03 1.32±0.03 1.31±0.02 1.32±0.03 1.32±0.03 1.30iO.03 1.35iO.03 1.36±0.03 135±0.03

c.s.
R.Q. R.Q. R.Q. R.Q. R.Q.

idem idem G3+53 G4+52 G4+S3 G4+S2 G4+53 G4+52 G4+S3 G4+S3 G3+S3 G4+52 G4+53 G4+S2 G4+S3 G4+S3 G4+52 G4+53 G4+S3~7 G4+S3 G3+53 G4+S2 G4+S3 G4+S2 G4+S3 G4+53 G4+52 G4+S3 G4+S3 G4+S3 G4+S3 idem G3+S3 G3+52 G3+53 G1+51 G3+52 G3+S3 G3+S2 G3+53 G3+S2 G3+S3 G1+S1 G3+52 GJ+SJ G3+S2 G3+S3 G3+52

15 6 6 15 15 21 30

R.Q. R.Q.

R.Q.

c.z. W"
R.Q.

720 720
720 720 770 720 770 720

RQ. R.Q. R.Q.
R.Q.

R'
R"

15 15 6 6 15 15 21 30 30 30

11.1 'l!" - 0,23±0.01

R.Q.
R.Q.

c.A. R'"
R.Q. R.Q.

720
770 720 720 720 720 770 720 720 720 720 770 720 720 720 720 720 770 770 720 770 770 720 770 770 720 770 770 770 720 770 770 770 720

c»:
RQ. R.Q. RQ. R.Q. R.Q. R' R.Q. R"

15 15 6 15 15 21 30 30 30 37 15 15 15 15 15 21 30 30

64.7±0.3 r-lO.25±0.1

c»:
R.Q. RQ. c.s. R.Q. R'"
R.Q.

RQ. R.Q.
R.Q.

R'
us

R.Q. R"

RQ. R.Q. R.Q. R.Q. RQ. R.Q. W R.Q. R"

15 15 15 15 21 30 30

c.A.
R.Q. R.Q. R.Q. R.Q. RQ.

R'

15 15 15 15

R.Q. R"

3-15 3-16

c.x.

Partitioning

of U between granite melt and aqueous Table 2. (Continued)

fluids

2501

Run

._----_._----_-- T days Nature gel
nb. 21 30 30 W 15 15 15 21 21 30 15 21 21 30 15 21 21 30 G+.. S C3+53 C1+51 G3+52 G3+SJ GJ+S2 C1+51 G1+S1 G2+54 Cl+51 G1+51 G1+51 G2+54 Gl+S1 G1+51 G1+51 G2+54 Gl+51
m_;e_g __ (_OC)

log f02 (b"_rJ -4.0 -4_0 -43 -4.0 -4.0 -15.0 -15.0 -15_0 -15.0 -10.3 -10.3 -10.3 -10.3 -4.0 -4.0 -4.0 -4.0

5iD2

A1203 w_t_%_ 11_0±0.1 10.6±0.1 11.1±0.1 lO.SiO.l 1 J.J iO.l 11.4±0.1 11.3±0.1 10.9±0_1 10.95±0.1 10.8±O.1 10.S±O.1 11.4±0.1 11.1±0.1 11.1±0.1 10.S±0.1 10.9±0.1 111.8±0.1

K20
wt%

U02
wt%

H20
wt%

K/(Na+K) (molal)

(Na+K'iAI (ITH·:::.1

-----3-17 3-18 3-19 3-20
3-21

"'_t

"_lo

RQ. RQ_ RQ_ R-Q_ R.Q. R"
R.Q.

136 1'1;; 166 184 ]59 166 186 156 163 156 189 156 145 166 159 158 175

770 770 720 770 770 770 770 770 770 770 770 770 770 770 770 770 770

69.0±0.2 70.2±0.2 68.6±OA 6S.5iO.2 6S.7iO.2 71.0±0.2 71.3±0.3 72.0±0.3 71.6±OA 72.45±05 72.4±O.l 71.1±0.3 72.3±0.3 71.4±0.5 72.0±0.5 71.7±0.3 72.3±03

3.610.1
(3.60)

6.5±O.1 (647) 6.2±O.1 6A±O.1 6.JiO.oS 6.45iO.05 5.l±0.05 4.9±O.1 4.5±01 4.7±0.1 4.2±0.05 4.32±O.OS 4.7S±O.05 4_8±0.05 4.6±0.04 4.2±0.05 4.5±0.05 4.55±0.05

0.34±0.02 0.34±0.02 0.31S±O.02 0.J3iO.D2 0.J6j:(J.02 0.014±0.001 (0.01331 0.016±O.001 (0.01671 O.OJ 5±O.001 (0.01671 '1.014±0.001 10.01421 0.034±O.001 10.01521 0.016±0.001 (0.01461 0.034±O.001 10.03291 0.033±O.001 )0.03151 0.057±0.001 (0.0579) 0.054±O.001 (0.05551 0.054±0.001 [0.05261 0.059±O.001 [O.OS74[

9.53 9.18 9.62 10.56 9.85 8.05 8.19 8.24 8.69 8.35 8.25 8.4J 7.62 8.57 9.17 8.97 8.24

0.27±0.0] 0.27±0.01 0_29±0.01 0.26iO.Ol O.26iO.Ol 0.36±0.0] 0.37±0.01 0.3910.01 0.37±0.0] 0.39±0.01 0.3910.01 0.37±0.01 0.35±0.01 0.37±0.01 OAO±O.Ol 0.37±0.01

1.33±0.03 132±0.03 1.335±O.03 J.30iO.02 1.295iO.02 1.15±0.02 1.12±0.02 1.11±0.02 1.11±0.03 1.060±O.024 1.0910.02 1.10±0.02 1.11±0.02 1.0910.02 1.0910.02 1.07±0.02

3.45±0.1 4.0±0_1 J.4iO.04 3.5iO.OJ 4.4±0.1 4.3±0.05 4.3±0.1 4.1±0.1 4.2±0.1 43±0.04 4.4±O.1 4.1±0.04 4.2±0.03 4.2±0.1 4.00±0.1 4.1±0.05

4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10

RQ. RQ_ RQ.
R.Q.

RQ. RQ. RQ. R_Q. R.Q. RQ.

4-11 c.A, 4-12
R.Q.

0.37±0.01-.1J.0±0.02

G : initial gel; G.A.

S

initial aqueous

solution.

Compositions pressure

01 gels and initial aqueous vessels as U308 (0.5-2.0 (0.45 %)and

solutions

are in table 1.

experiments initial

using conventional using rapid quench gel in milligrams

autoclaves cold-seal

R.Q. : experiments gel (mg) W R" W" u.s. : experiments reversal reversal
wt

using granite gel undersaturated using granite using granite determined

with uranium solutions instead tracks

Na2G03 (VI)

solutions.

experiments experiments

and Na2C03 (or schoepite) by global

oversaturated

with uranyl

gel doped with U308 analysis

wt%) and NaZG03 glass using atomic

solutions. absorption spectrometry.

o.

: experiments % of Na20

using excess of U308 and K20

01 excess 01 U02.

01 silicate

[] : wt % of U02 in silicate glass determined

by lission

solubility in the silicate melt of several orders of magnitude (Table 2; Fig. 3b). However, the effect of fo, on the uranium solubility in the silicate melt progressively decreased with increasing ex from 1.1 to 1.5. In very peralkaline silicate glasses ( I.5 < IX S 1.7), the role of both f02 and IX on the uranium solubility becomes negligible (Fig. 5). The limited temperature increase from 720 to 770°C did not appear to affect significantly the behaviour of uranium in silicate melts. The uranium solubility curves as a function of log fo, and IX were fitted using least square method with the Eqn. 5: log (U) (ppm)
=

buffers Ni-NiO, Fe304-Fez03, and CUzO-CuO, the uranium solubility can be expressed by Eqn. 6:
109

(U) (ppm) = 0.04 log

f0

2

(bar)

+ 3.80a

- 1.34.

(6)

Eqn. range three lation

6 is valid for 720 s T s 770°C at 2 kbar. For a in the 1.5-1. 7, the three uranium solubility curves for the above cited oxygen buffers were obtained by interpoof analytical data.

at log fo, (bar)

The Distribution of Potassium and Sodium Between Carbonated Aqueous Fluid and Silicate Melt
2

+ a-« + a3log f0

(bar) a

+ a4.

(5)

In all cases, the term a310g fa, (bar) IX was negligible. For IX in the range 1.1-1.5 and for log fo, values fixed by three

Earlier works on the distribution of potassium and sodium between haplogranite and chloride solution at 700-800°C, 1.4-2.4 kbar have reported that potassium tends to concen-

2502

C. Peifiert, ivL Cuney. ar d C. Nguyen-Trung

---I

E
'-'

Q..

a.

~ CuZO-CuO

°

Fe304-Fe203 Rev. Exp.

o Ni-NiO

+

• Yudintsev

1.0

1.2

1.4

1.6

1.8

(Na+K)/AI
FIG. 5. Uranium solubility (ppm) in granitic silicate melt vs. agpaitic coefficient a = (Na + K)/ AI under /0, fixed by Ni-NiO, Fe304Fe203, and CUlO-CUO buffers. Comparison with Yudintsev's data in granitic silicate melt in contact with H20 (Ni-NiO buffer) (1990) (.).

--

.

trate in melt, whereas (GAMMON et ai., 1969; GACHE, 1980). These relation between two (Eqn.7): FK

sodium prefers the aqueous fluid HOLLAND, 1972; CARRON and LAauthors also established a simple ratios [K/Na]melt and [K/Na]nuid

should be very low and in the range of ppb. In contrast, ZHARIKOV et al. (1987) and YUDINTSEV (1990) have reported that the uranium solubility in a mixture uranium oxide, H20, and haplogranite at 750°C, 2 kbar, and fo, condition fixed by Ni-NiO buffer increased from 1.5 to 14 ppm U for exincreasing from 0.78 to 1.4. These values are three to four orders of magnitude higher than the ppb uranium value extrapolated from solubility measurements by RED'KIN et a!. ( 1989) and up to one order of magnitude higher than those determined in carbonated solution ( 1-2 ppm) in this study. The high solubility of uranium obtained by ZHARIKOV et a!. (1987) and YUDINTSEV ( 1990) was probably due to the presence of small amounts of uranium solid or U-bearing silicate glass in nonfiltered H20 after the runs . In the present study, the low uranium solubility (1-2 ppm) obtained under reducing conditions (Ni-NiO, Fe304-Fe203 buffers) was principally due to the low solubility of U (IV) complexes with OH - and CO~- ligands. The relatively high uranium solubility (17 ppm) determined under oxidizing conditions (Cu20-CUO buffer) probably originated from two dependent factors: (1) the high solubility ofU(VI) (25 mol%) contained in U0(2.25±002), the solid phase in equilibrium with the aqueous fluid, and (2) the formation of more soluble U(VI) complexes with OH- and mainly CO~- ligands in aqueous fluid. The Behaviour of Uranium in Silicate Melts The behaviour of uranium in anhydrous silicate melts is different from that in aqueous solution. Three stable redox states of uranium-c-I Vl ), (V), and (IV)~characterized by yellow color, colorless, and green color, respectively, coexist in melts (CALAS, 1979; SCHREIBER, 1983; FARGES et a!., 1992). The equilibrium distribution ofU(Vl), U(V), and U (IV) is dependent on the imposed fo, (CALAS, 1979; SCHREIBER, 1983; YUDINTSEVet al., 1990) and the alkalinity of the silicate melt (CALAS, 1979; SCHREIBER, 1983). Recent works of FARGES et al. ( 1992) have indicated that ( 1) U (VI) occurs as linear urany}, U V10~+, with four to five equatorial bonds to oxygen, (2) U (V) exists in 6-coordinated sites under moderately reducing conditions (above the QFM buffer), and (3) U (IV) is present in 6-coordinated sites under reducing conditions (below the Ni-NiO buffer). U(VI), U(V), and U (IV) are likely to bond to nonbridging oxygen (NBO). Thus, the amount ofNBO is considered as a factor controlling the uranium solubility in anhydrous silicate melt. The increase of peralkalinity greatly contributes to depolymerize the aluminosilicate network and thus increases the production of NBOs (MYSEN, 1988). Consequently, the solubility of uranium is enhanced by increasing peralkalinity of the silicate melt (FARGES et ai., 1992). In contrast, little is known about the behaviour of uranium in water-bearing silicate melt. This is due to the lack of reliable data on uranium speciation in hydrous melts and analytical difficulties. Earlier experimental works have established that the dissolution of water in silicate melt depolymerizes the aluminosilicate network. Numerous solubility mechanisms for water in silicate melt have been proposed (BOWEN, 1928; BURNHAM, 1975; OXTOBY and HAMILTON, 1978; MANNING et al., 1980; MYSEN et al., 1980; STOLPER, 1982; EPEL'BAUM,

c

=

[K/Nalmelt (K/Na]nuid

=

1.2-1.7.

(7)

In the present study, FK values determined from [K/Na] data (Tables 2 and 3) are in the range 2.5-6.2. These results are up to 3.6 times larger than those determined in a chloride system. Apparently, the carbonate ligand has a stronger affinity with sodium than with potassium and thus contributes to enhance considerably FK value.
DISCUSSION

The Behaviour of Uranium in the Aqueous Fluids Earlier works (ZHARIKOV et al., 1987; KEPPLER and WYLLIE, 1990, 1991) have reported amou nts ranging from 12 to 1100 ppm U in HCl, HF, H20 + CO2, and (Na, K)Cl aqueous solutions in equi.librium with U-bearing haplogranite (0.78 5 ex s: 1.08) at 750°C, 2 kbar, under Ni-NiO or Fe304Fe203 buffers. The higher uranium content resulted from the acid pH and/or the large concentration of halides in the aqueous fluids, compared to the low uranium solubility ( 13 ppm) in carbonate solutions under similar fo, conditions in the present work. RED'KIN et al. ( 1989) reported that the solubility of UOl in H20 at I kbar and under reducing conditions (Ni-NiO buffer) increased very slightly from 0.24 ppb U (10-9 mol) to 0.75 ppb U ( 10 -8.5 mol) for temperature increasing from 300 to 600°C. From this result and based on the fact that U02 does not undergo any phase transformation up to its melting point (~2800°C) and 2 kbar, it is very probable that the solubility ofV02 in reduced water up to no°c, 2 kbar

~

. __

.

~_.

__ .~.

•__

... _

• __ ~e

···_·e_.

Partitioning

of U'between

granite melt and aqueous

fluids

2503

1985). Based on above-mentioned models and recent Raman works of MYSEN and VIRGO ( i 986a,b), MYSEN ( 1988) suggested that water enters the aluminosilicate melts in the form of molecular H20 and OH-complexes bonded to both A13+ (non-tetrahedral) and Na +. The formation of Si-OH and (Si, AI)-OH was not evidenced. For felsic liquids, with AI/ (AI + Si) < 0.2, essentially all the OH ligand is associated with alkali metals and H20 is dissolved in two principal forms: alkali-OH groups and molecular H20 (MYSEN, 1988 ).In the present study, as the ratio AI/(AI + Si) was in the range 0.13-0.16, molecular H20 as well as Na-OH and K-OH groups are three major forms of dissolved water (8-13 wt%) in melts. Although the mechanisms of uranium solubility in hydrous silicate melt is not quite understood, the low uranium solubility ( 100-300 ppm) in low alkaline content hydrous melt (a = 1.1) indicates that the formation of stable complexes between various forms of dissolved water and uranium is improbable. The formation of stable U(IV), (V), and (VI) carbonate complexes was also improbable because the concentration of dissolved CO2 in silicate melt was low ( ~ I 100 ppm), constant, and independent of uranium concentration. Consequently, like the alkalinity, the only major effect of dissolved H20 in silicate melts on the uranium solubility is the production of the NBO due to the depolymerization of aluminosilicate network. The redox conditions of the system also play an important role in the uranium solubility. Earlier works have established that increasing oxidation enhances uranium solubility in anhydrous silicate melts (CALAS, 1979; DOMINE and VELDE, 1985; YUDINTSEV, 1990). In addition, uranium solubility measurements in sodium trisilicate glasses iIY'~ted that U(V) and U(VI) are four times more soluble than U(lV) (VEAL et aI., 1987). Results obtained in the present study confirmed the positive effect of redox conditions (log fa,) and agpaicity (a) of the melt on the uranium solubility in a water-bearing haplogranite melt.

solubility is considerably reduced (Fig. 5). The origin of the change of the behaviour of uranium is not yet understood. The uranium solubility has been determined in a haplogranite melt, in contact with uranium oxide and H20, at similar P, T, and f02 (Ni-NiO buffer) conditions (ZHARIKOV et a!., 1987; YUDINTSEV, 1990). These authors reported increasing uranium solubility from 3 X 102 ppm to 104 ppm with a increasing from 0.78 to 1.60. For a = 1.1, a disagreement exists between data obtained by ZHARIKOV et a!. (1987) (5.5 X 103 ppm) and by YUDINTSEV (1990) (2 X 103 ppm). These results are one order of magnitude higher for a = 1.1 and slightly lower for a ? 1.5 than our results (Fig. 5). The higher uranium solubility, obtained from bulk analysis, may result from the heterogeneity (e.g., presence of small amounts of urani urn solid) in silicate melts after the runs. The Partitioning of Uranium Fluid and Silicate Melt Between Carbonated Aqueous

The partition coefficient (DFlu;d/MClt) of uranium between carbonated aqueous fluid and silicate melt increases linearly with increasing log fo, from -15 to -4 by about 0.5 order of magnitude, for a in the range 1.1-1.5 (Fig. 6; I-III; Table ....3). The D increase becomes slightly more important for a ~ 1.7 . For a given f02, the decrease of a from 1.7 to 1.1 leads to an increase oflog D of about two orders of magnitude. Raising the temperature from 720 to no°c does not significantly affect D. The variation curve of log D Flu;d/Melt vs. log fa, and a was fitted using the least square method with the Eqn. 5. Similarly, the term a3 log fo, (bar) a in Eqn. 5 was negligible. For a in the range 1.1-1.7, log D Flu;d/Melt vs. log fo, and a can be expressed by Eqn. 8: log
DFlu;d!¥-"U

=

-3.78a

+ 0.05

log fa, (bar)

+ 2.84.

(8)

Redox conditions
Under reducing conditions (Ni-NiO buffer), the low uranium content may result from the low solubility of U(IV) present with U (V) in colorless glasses. Under higher f02 conditions (Fe304-Fe203, Cu20-CuO buffers), the higher uranium concentration originates from the higher solubility of uranium (V) and mainly uranium (VI) characterized by yellow glasses (Fig. 3 and 5).

Agpaicity of silicate melts (a)
For a given log f02 value and an amount of dissolved water (8-13 wt%), the uranium solubility (log U) increases linearly up to two orders of magnitude with increasing a from 1.1 to 1.5 (Fig. 5). The additional production ofNBOs, due to the increase of alkalinity or agpaicity (ex = (N a + K) / AI), is likely to be responsible for the enhancement of the uranium solubility. The effect ofagpaicity on uranium solubility is up to 25 times more important than that of f02. In highly peralkaline silicate melts (ex = 1.7), the effect of both factors (redox conditions, agpaicity) on the uranium

Validity conditions ofEqn. 8 are similar to those ofEqn. 6. The low D values obtained in the present study clearly indicated that most of uranium is preferentially concentrated in the silicate melt, particularly in peralkaline melt under oxidizing conditions. . Values of partition coefficient (DFlu;d/Melt) of uranium, determined between a haplogranitic melt and aqueous fluids containing variable amounts of HCl, HF (ZHARIKOV et a!., 1987; KEpPLER and WYLLIE, 1990, 1991), H20, H20 + CO2 (ZHARIKOV et aI., 1987; KEpPLER and WYLLIE, 1990, 1991; YUDINTSEV, 1990), or (Na, K)Cl, or (Na, K)F (ZHARIKOV et aI., 1987; YUDINTSEV, 1990) at similar P, T, fo, (Ni-NiO or Fe304-Fe203) conditions, were four orders of magnitude higher than those determined in the present study (Fig. 6). The discrepancy could originate from the differences in composition of the aqueous fluid (pH, ligand) and silicate melt. However, as the composition of the uranium solid phase, silicate glass, and aqueous solution after the run were not reported in most cases (KEpPLER and WYLLIE, 1990, 1991; YUDINTSEV, 1990), a detailed discussion of these data is not possible. GEOLOGICAL 1MPLICA TIm'iS Results obtained in the present study provide greater understanding of the fractionation of uranium during magmatic

1504
Table 3. Chemical and partitioning

C. Peifiert, M. Cuney, and C. Nguyen-Trung composition of uranium of aqueous between fluid after fluid run and silicate melt

aqueous

Run 1-1 1-2 1-3 1-4 1-5 Hi 1-7 1,'3 1-9 1-10 2-1 2-2 2-3 2-4 2-5
.;

Nature C+5 C.A. RQ. R.Q. R.Q. F F F F Fidem Fidem X Fidem Fidem idem G3+S3 G4+52 G4+S3 G4+52 G4+S3 G4+52 G4+53 G4+53 G3+S3 G4+S2 G4+S3 G4+52 G4+S3 G4+S3 G4+S2 G4+S3 G4+53 G4+53 G3+S3 G4+S2 G4+S3 G4+52 G4+S3 G4+S3 G4+52 G4+53 G4+S3 G4+53 G4+S3 idem G4+52 idem idem idem

ago sol. .mg 120 126 129 152 146 138 142 147 133 131 254 105 133 109 133 102 123 124 256 166 136 113 145 110 106 112 145 7.85 281 145 123 126 145 133

T
(OC)

Jog f02 pH
(bar) -15.6 -15.0 -15.0 -10.3 -10.3 -10.9 -4.0 -4.0 -4.0 -15.0 -15.6 -15.0 -15.0 -15.6 -15.6 -15.6 -15.6 -75.6 -10.3 -10.9 -10.3 ·10.9 -10.9 ·10.3 -10.9 -10.9 -70.9 ·10.9 -4.0 -4.3 -4.3 -4.3 -4.3 -4.0 -4.3 -4.3 -4.3 -4.3 ·4.3 -4.0 ·15.0 ·15.6 ·15.0 -15.0 ·15.6 ·75.0 -75.0 - HI.9 -10.3 -10.3 -10.3 -10.9 ·10.3 8.8 8.7 8.9 8.5 8.1 8.7 8.7 8.9 8.6 8.5 8 ..1 8.4 8.7 8.5 8.6 8.3 8.7 8.8 8.7 8.9 8.6

Na ppm

K ppm

IC03 ppm

U ppm 1.06 0.86

K/(Na+K)

Dfluid/melt 4.26£·05 3.24£-05

720 770 770 770 770 720 770 770 770 770 720 770 770 720 720 720 720 720 770 720 770 720 720 770 720 720 720 720 770 720 720 720 720 770 720 720 720 720 720 770 770 720 770 770 720 770 770 720 770 770 770 720 770

1125

145

0.91 2.85 2.98

0.070

3.33£-05 1.02£-04 1.05£-04

c:«.
RQ. R.Q. RQ. R.Q.

983

185

2.10 13.02 12.87 12.65 0.12

0.100

7.71£-05 4.38£-04 4.33£-04 4.28£-04 3,00£-05

R.Q. us, X R.Q.
R.Q. R.Q.

F F F R'" F+ F R* R*' X SI F R*u X F+ F SI R* R*' F F F+ F F+ X

897 1104

113 153

0.88 0.91

0.069 0.075

9.25£-05 1.06£-04 1.29£-04 1.08£-04 1.27£-04

C.A. R.Q. RQ. R.Q. R.Q. R.Q. R.Q. R.Q.

1.05 0.92+0.01 4152 705.3 1.10
7.10

"

z-s
2-7 2-8 2-9 2-10 2-11

744

0.074

1.37£-04 9.5S£-05 2.30[-04 2.24£-04

0.80 2.')1 2.59+0.02 967 132 3.15 2.77 1276 7839 3.08+0.03 2.40 2.67+0.02 4.50 2.80 1223 12') 11.21 9.80+0.05 659 10.43 12.61+0.11 11.92 12.10 945 124 10.31 12.61+0.09 13.26 8.75 1.60 2432 898 113 0.85 1.41 1.75 1.70 1.62 2.67 0.97 4.70 2767 1156 215 2400 3.44 2.33 3.33 3.40 0.099 0.069 0.072 0.0.17 0.074

2-12
2-13 2-14 2-15 2-16 2-17 2-18 2-19 2-20 2-21 2-22 2-23 2-24 2-25

c.A.
RQ. RQ. C.A. R.Q. R.Q. R.Q. R.Q. RQ. R.Q. C.A. RQ. R.Q.

2.43£·04 2.17£-04 2.31£-04 1.82£·04 2.01£·04 3.84[-04 2.04t:-04 5.30£·04 5.29£-04 5.40£-04 6.53£·04 6.06£-04 6.20£·04 5.49£·04 6.56£-04 7.48£·04 4.11£-04 4,00£-04 1.00£-03 1.45£·03 1.60£-03 1.61£·03 1.53£-03 3.61 £-03 8.73£·04 3.39E-03 2.47£-03 1.71£·03 2.36£-03 2.74£-03

c.A.
R.Q. RQ. R.Q.
R.Q.

F R"""
51 R' R
U

122 114
166 133 123 163

2-26
2-27 2-28 2-29 2-30 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3,'3 3-9 3-10 3-11 3-12 3-13

R.Q. R.Q. RQ. RQ. R.Q. R.Q. R.Q. R.Q. R.Q.

us,X F X F F X R' R" X F X F X R' G3+S3 G3+S2 G3+S3 Cl+S1 G3+S2 G3+S3 G3+S2 G3+S3 G3+S2 G3+S3 C1+51 G3+52 G3+53

163 122 150 170 127 160 122 123 124 133 123

c:«.
RQ. R.Q. R.Q. R.Q.

122
112

Partitioning of U between granite melt and Table 3. (Continued)
Run Ivatu re G+S 3-14 3-15 3-17 3-18 3-19 3-20 3-21 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 -~ 4-11 4-12 R.Q. R.Q. RQ. R.Q. RQ. R.Q. R.Q. R.Q. R.Q. R.Q. R.Q. R.Q. R.Q. R.Q. R.Q. R.Q. RQ. R.Q. CA. R.Q. F+ X F F F+ X X F X F F Cl +SJ C2+S4 Cl 156 125 770 770 770 770 770 770 770 770 770 770 770 -15.0 -15.0 -15.0 -10.3 -10.3 -10.3 -10.3 -4.0 -4.0 -4.0 -4.0 942 178 8.7 8.2 945 212 8.3 R" X F F X F R> R" F G3+S2 G3+S3 G3+S2 G3+S3 aq. sol. mg 110 262 144 145 116 123 792 710 163 T (ec) 770 770 720 770 770 720 770 770 770 log f02 pH (bar) -10.3 -4.0 -4.3 -4.0 ~1.0 -43 ·4.0 -4.0 -15.0 1026 185 8.7 8A 8.5 867 206 Na ppm K ppm

aqueous

fluids

2505

IC03
ppm

u
ppm 2.92

K/INa+K)

OOuid/melt

0.123 15.87 15.27 16.95 14.52 76.50 9.77 1.32 0.98+0.01 1.21 1.16 3.33 3.05+0.02 2.98 2.78 13.21 13.02 12.65 12.26 0.100 0.117 0.096 5.14E-03 5.14£-03 5.64E-03 4.921:-03 5.66£·03 3.04£-03 1.05£-02 7.13E-03 9.21E-CB 9.54£-03 1.11 E-02 9.58E-03 9.70E-03 9.6SE-CB 2.63E-02 2.73£-02 2.68E-02 2.36[-02

3-16 CA.

er-st
G3+S2 G3+S.l G3+S2 Cl+S1

-s:

134

G1+S1

123 143 112 133 134 112 123 146

ci -si
C2+S4

ci-si
C1+S1 C1+S1 C2+S4 Gl+S1

G C.A. R.O.

initial gel ,5 experiments : experiments

initial aqueous

solution.

Compositions pressure

01 gels and initial aqueous vessels (0.45 %) and Na2C03 oversaturated (0.5-2.0

solutions

are in table 1.

using conventional using rapid quench aqueous using granite

autoclaves cold-seal solution in milligrams with U308 solutions. (VI) solutions. solutions with uranyl

aq. sol. (mg) W reversal reversal solubility solubility amount experiment'

initial Na2C03 experiments experiments

u.s. : experiments

gel undersaturated

using granite using granite of U308

and Na2C03 (or schoepite) aqueous solution aqueous

W'
X F F+ 51

gel doped with U308 solution

wt%) and Na2C03

R'" : experiments

using excess

instead of excess of U02.

measurements measurements of uranium

of unfiltered of liltered aqueous

solution and 01 filtered purified solid particles quartz grains containing

of filtered

using an additional

Pt capsule

differentiation, vapor oversaturation of the felsic magmas, and the formation of magmatic uranium deposits. 1) The experimental results show that uranium solubility is very high in peralkaline felsic melts (102 to 2-3 X 104 ppm U). Thus, pera1kaline magmas represent extremely efficient vectors for uranium transfer from the mantle to the upper crust. The much lower uranium content measured in natural peralkaline rhyolitic glasses (a few tens of ppm) with agpaitic index values up to 1.9 (CHRISTI.·\NSEN et al., 1983; KOVALENKO et aI., 1989) indicates that these melts are strongly undersaturated with respect to uraninite. Thus, during magma fractionation, uraninite

will not present an early crystallization. These results explains the strong incompatible behaviour of uranium during magmatic processes as observed for example by NOVAK and MAHOOD ( 1986), VILLEMANT et al. ( 1980), and VILLEMANT and PALLACIN (1987) in volcanic rock suites. 2) The high uranium solubility in peralkaline silicate melts will lead to a steady enrichment of this element during fractional crystallization. This behaviour may lead to the formation of large magmatic uranium deposits in association with the most fractionated melts of the peralkaline igneous complexes. Such a mechanism is best illustrated

-----------

-----------------------------------_

.._. __

.

C. Pciffert, M. Cuney, and C. Nguyer.-Truug

o -----------------------------,

3

-1

5 7 8 10

.. .. e .. ..
c

2 4 6

e

9

CJ.

=
=

1.1
D

-2 CJ.

1.3
E F

-3

CJ. = CJ.=

1.5
1.7
F

-4

-5+---~~---.----~----.---~----.-----~--~
-20 -15 -10 -5

o

log £02 (bar)
FIG. 6. Correlation between partition coefficient of uranium (log Dfluid/mdt) and log /02 (bar) (square: Ni-NiO; circle: Fe)04-Fe20); triangle: Cu20-CuO) for agpaitic coefficient a = 1.1, 1.3, 1.5, and 1.7. Comparison with data reported by (a) KEpPLER and WYLLIE (1990): (I) HF 4 m, (2) HF 3 m, (3) HF 2 rn, (5, 6, 8) HF I m; (4) 2 m HCI, (7) I.S m HCI, (11)0.5 m HCI, (12) 1 m HCI, (15) 0.5 m HCI, (16) 0.5 m HCI; (9) 2.5 m CO2, (10) 5 m CO2, and (b) YUDINTSEV (1990) (a = (Na + K)jAI = 1.4): (17) I m C02i"#4) 0.1 m NaosKosF; (13) I m NaosKosCI, at 750°C, 2 kbar, and /0, fixed by Ni-NiO buffer.

-_

lujavrites of the K vanefjeld deposit in the Ilimaussaq peralkaline complex, Greenland, which represent the most highly fractionated melts of the complex with the highest agpaitic index. The highest uranium content is reached in the medium-coarse grained lujavrites with an average U content of 400 ppm for an agpaitic index of 1.5 (S0'RENSEN et al., 1974). Local enrichment up to 1550 ppm remains far below the saturation levels for such melts determined in the present work: about 104 ppm for an agpaitic index of 1.5. 3) Peralkaline granitic magma can dissolve uranium up to 104 time more than an aqueous carbonated fluid at equilibrium. The amount of uranium in a H20-C02 magmatic fluid coexisting with peralkaline magmas is very small (1-15 ppm). Consequently, uranium fractionation in magmatic fluids during magma vapor oversaturation will not affect the uranium content of the original magma for peralkaline melt compositions and aqueous carbonated fluid (log DF1uid/Melt = -4). The effect may become important during peraluminous magmas fluid oversaturation in oxidizing conditions. According to the results of KEpPLER and WYLLIE ( 1991 ) and the occurrence of uraniumfluorite-rich veins spatially associated with peralkaline intrusions such as Ilimaussaq (S0'RENSEN et al., 1974), this effect should be much more important for F- and! or CIrich fluids,

by the mineralized

of the high-pressure and temperature experiments were done in the Experimental Laboratory of the Centre de Recherches Petrographiques et Geochimiques (CRPG) =-France. The authors thank A. Rouillier, M. Vernet, F. L'hore (CRPG), J. M. Claude (Univ. Nancy J), and M. Canals (CREGU) for their technical and analytical support, We acknowledge detailed and thoughtful reviews by GCA reviewers: Dr T. Latourette, Dr B. Mysen, Dr D. Shaw, and Dr B. Velde.

Acknowledgments-Most

Editorial handling: D. M. Shaw
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posits", Vienna, 49-60.

BOWEN N. L. (1928) The Evolution of the Igneous Rocks. Princeton Univ. Press. BURNHAM C. W. (1975) Thermodynamics of melting in experimental silicate-volatile systems. Geochim. Cosmochim. Acta 39, 10771084. CALAS G. (1979) Etude experimentale du comportement de l'uranium dans les magmas, etats d'oxydation et de coordinance. Geochim. Cosmochim. Acta 43, 1521-153!. CARRON J. P. and LAGACHE M. (1980) Etude experimentale du fractionnement des elements Rb, Cs, Sr et Ba entre feldspaths alcalins, solutions hydrothermales et liquides silicates dans le systcme Q.Ab.Or.H20 2kbar entre 700 et 800°C. Bull. Mineral. 103, 571-578.

a

Partitioning

of U between granite melt and aqueous

fluids

2507

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I
I

I'

i !
J'f
j

" I'

I:

I

I

I II
1

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