Gmchimica CI Cosmuchimia Ada Vol. 51: pp.

4419-4434
Copyright B 1993 Pergamon Piss Ltd. Pnnted inU.S.A.

Mobilization and redistribution of REEs and thorium in a syenitic lateritic profile:

A mass balance study
JEAN-JACQUESBRAUN, Q* MAURICE PAGEL, ’ ADRIEN HERBILLON,*and CHRISTOPHE ROSINS
‘CREGU and GS CNRS-CREGU, BP23,54501 Vandwwre-&-Nancy Cedex, France
‘Centre de Pkdologie Biologique, CNRS, BP5, 5450 1 Vandauvre-l&-Nancy Cedex, France
‘IRHSP, 1lbis rue Gabriel P&i, 54500 Vand~uvr~l~Nan~, France

(ReceivedAugust 11, 1992; accepted in revisedform April 1, 1993)

Abstract-REE-Th geochemistry and mineralogy have been studied in a lateritic profile derived from a
syenite at Akongo in SW Cameroon. REE and Th mass balance caiculations for the host-rock minerals
show that at least 70% of the LREEs and 50% of the HREEs are contained in allanite, apatite, titanite,
and epidote and at least 50% of the Th is controlled by the same accessory minerals which represent
about 2 wt% of the unaltered syenite. These accessory phases are destroyed during the first stages of
weathering causing most of the REEs and Th to be rapidly released into the soil.
Comparison of the variation in the Zr, Ti, and Th content as a function of the apparent density of the
different zones of the saprolite shows that Th is the least mobile element. The presence of secondary
thorianite (ThOz), the etched surface on zircon 8rains, and the presence of Ti in secondary cerianite
support this geochemical inte~~tation. The ~n~ntration of thorium was, therefore, chosen as invariant
relative to the concentration of the other elements, especially the REEs, in mass balance calculations.
Most of the REEs are leached in the iron-rich upper horizons (loose nodular horizon, iron crust, and
top of mottled clay horizon). Where the ~oundwater table moves (saprolite and bottom of the mottled
clay horizon), the REEs are fractionated and redistributed. There is a juxtaposition of leached and
accumulation zones with precipitation of LREE aluminous hydrated phosphates.
This study supports the existence of two different cycles for the redistribution of elements in the soil:
( 1) as dissolved ions in the saprolite horizon, and (2) as individual particles in the upper part of the
profile.

INTRODUCTION weathering processes ( PIJLER and ADAMS, 1962, LANGMUIR

and HERMANN, 1980) due to its very low solubility in aqueous
ONEPOSSIBLEWAYTOSTUDY~~~ geochemicalbehavior of
solution ([Th] seawater = 7. lo-” pg.1-l: KAUFMANN,
REEs during weathering is to choose a parent rock with REE
1969) which may, however, increase by complexation with
contents neighboring on the ZREE average content of the
organic ligands and because (2) the Th and REE distribution
Earth’s continental crust (about 150 ppm; HENDERSON,
in plutonic rocks is essentially controlled by the same acces-
19841, and a weathering en~~nment where the mobili~~on
sory minerals whose weight proportions are often less than
and redistribution processes can be identified. Lateritic soils
1%( FOURCADE~~~ALLEGRE,~ 981; PAGEL,1982;G~o~E~
developed on plutonic rocks are of prime interest because of
and SILVER, 1983).
( 1) the relative ease with which the parent rock minerals can
The behavior of REEs and Th during rock weathering de-
be identified, and (2) the contrasting behavior of the chemical
pends on the intensity of weathering and the stability of pri-
elements during intense lateritic weathering.
mary minerals (TAYLOR and MCLENNAN, 1985; MCLEN-
The mobilization and redistribution of REEs during
NAN, 1989). In the weathering products, REE and Th may
weathering, reflecting the water/rock interaction processes,
be immobilized by various m~hanisms such as (i) retention
can be defined using mass balance calculations that take an
in primary minerals which are resistant to weathering, (ii)
immobile element as an invariant ( NESBITT, 1979, CRAMER
incorporation in newly-formed crystalline or amorphous
and NESBITT,1983; MIDD~LBURG~~~~,~~~~;BRIMHALL~~
phases, and (iii) adsorption by clays.
al., I99 I ). The chosen immobile element must have certain
The Akongo lateritic profile (SW Cameroon), previously
properties including ( 1) a very low solubility in aqueous so-
studied for Ce-anomalies ( BRAUN et al., 1990) and containing
lution, (2) inclusion, if possible, in resistant primary minerals,
a ferricrete which developed on a syenite, was chosen for this
and (3) a homogeneous distribution in the parent rock. Ti-
study. This is a representative profile of lateritic weathering
tanium and zirconium are the elements which are the most
encountered in Central Africa under humid climatic condi-
often used for such calculations (e.g., NESBITT,1979; MID-
tions and forest cover.
DELBURG et al., 1988). However, CRAMER and NESBITT
First, a petrological and quantitative mineralogical study
( 1983) have proposed the use of other highly charged trace
of the parent material was conducted to determine the min-
elements such as SC, Th, and Hf.
erals which initially control the REE and Th distribution.
Thorium was selected here to be tested as an invariant
Then, the transformation between the least altered syenite,
both because ( 1) it is among the least mobile elements during
the weathered syenite, and the saprolite was examined. This
provided information on the weathering petrography, es-
* Present address: ORSTOM, BP 1857 Yaoundi, Cameroon. pecially ofaccessory minerals, and the chemical composition
4419
4420
of secondary REE and Th-bearing minerals within the ac-
cumulation zones, created by either in situ formation after
the primary phase breakdown or by direct deposition from
soil solutions. Finally, the changes in elemental abundances
in the soil samples relative to those in the parent rock have
been calculated. These mass balance calculations allow a
comparison of the movement of the REEs and Th on the
local scale to that of the elements ( 1) which characterize the
main lateritic features (Si, Al, Fe, . . .) and (2) which are
generally considered as immobile during weathering (Zr, Ti).
DESCRIPTION OF THE PROFiLE
The studied profile, partly described in BRAUN et al.
( 1990), is located at the top of a syenitic hill. It is five meters
deep and displays four different horizons (Fig. i ). From bot-
tom to top, the principal structural and mineralogical features
of the horizons are the following:
1) A saprolite, 100 cm thick, which is composed of two do-
mains with distinct structures. The first domain corre-
sponds to the sandy weathering products of the syenite
in which the preexisting rock texture and structure are
preserved. These zones are generally lens-shaped. They
present more or less weathered syenitic boulders sur-
rounded by a loose yellow sandy material which becomes
redder towards the edges of the lens and the top of the
saprolite. The red coloration is due to the increasing in-
dividualization of goethite and hematite after the break-
down of ferromagnesian minerals. The lenses showing a
gradual weathering are embedded in a second domain
composed of a network of anastomosing white clayey
seams. A more detailed description of the seams along
the profile is given next. The bottom of the saprolite is
composed of a syenite flag which is already weathered.
The saprolite shows a gradual, undulating, and discon-
tinuous upper limit.
2) A mottled clay horizon, 75 cm thick, consisting of jux-
taposed red decimeter-size and white centimeter-size do-
fiG. I. Representation of the studied top-&If profile developed on
the Akongo syenite.
J. J. Braun et al.
mains. The red domains (RD) are soft, isolated ferrugi-
nous mottles in which the parent rock texture can still be
recognized. Goethite, hematite, and kaolin&e are the main
constituents. White domains (WD) are soft and are
mainly composed of kaolinite. The upper limit of this
horizon is undulating.
3) An iron crust, 230 cm thick, composed of a purple red,
ferruginous, and indurated material crossed by a network
of ochre-yellow and white, soft and porous spots. In this
layer, the parent-rock structure and texture have com-
pletely disappeared. The upper limit is gradational.
4) A loose nodular ferruginous horizon, 90 cm thick, in
which indurated hematitic nodules are surrounded by
yellowish brown, mainly kaolinitic, materials. Near the
surface, organic matter accumulates down to 5 cm.
The White Clayey Network
The seams represent pre-existing joints where clayey ma-
terials have been both deposited and precipitated. In the sap-
rolite and the mottled clay horizons, the seams of massive
structure are essentially composed of halloysite with residual
primary minerals such as microcline, magnetite, and zircon.
At the bottom of the saprolite, the seams are extremely po-
rous. Open cracks up to 2 mm are present. In the middle
part of the saprolite, the seams are continuous, well-individ-
ualized, and with low porosity. Their margins are marked by
thin iron oxide coatings. The fissures situated within the seams
are coated by cutanes which are related to the circulation of
clays in suspension and their oriented deposition on the l&sure
walls. At the boundary between the saprolite and the mottled
clay horizon, the seams are packed and cut by mottled dayey
material. in the mottled clay horizon, some packed relicts of
the seams delimit three zones called a, b, and c (Fig. I). The
seam residues disappear towards the top of the profile and
their composition becomes more kaolinitic.
The Water Table
Significant annual fluctuations in the water table have been
measured in the Akongo pit ( BILONG,1988). During the wet
seasons (chiefly from March to July and from September to
October) the water Ievel reaches the lower third part of the
mottled clay horizon. The water table vanishes from the pit
during prolonged dry periods (Fig. 1).
SAMPLING
Mass balance calculations for trace elements such as REEs
and Th require the sampling of representative amounts of
material to minimize the errors due to the possible hetero-
geneous dist~bution of REE- and Th-bearing accessory min-
erals in the whole rock. The sampling of the parent material
and soil is described next.
1) Freshest and weathered syenites. The distinction between
the freshest syenite (FSY), which is the geochemical ref-
erence of this study, and the weathered syenite (WSY) is
based on the cohesion of the rock and the freshness of
the clinopyroxene crystals. These crystals, in the freshest
syenite, are free of iron oxyhydroxid~ and oxides. About
 Geochemistry of REEs and Th in a lateritic soil profile
I5 kg of the fresh and weathered rocks w&e sampled in
the bottom flag of the saprolite.
2) Saprolite (including sandy domains and white clayey
seams). During the sampling of the sandy domains, dis-
tinctions were made based on the color of the weathering
products which allow two weathering stages to be distin-
guished: a less weathered, yellow saprolite (YSAP) and a
more weathered red saprolite (RSAP). About 15 kg of
each were sampled. Only three samples of the white clayey
seams ( WCSl, WCSZ, WCS3) (weighing about 200 g
each), situated in the middle part of the saprolite, were
taken for complete analysis. They represent the seams
showing the largest positive Ce-anomalies ( BRAUNet al.,
1990).
3) Mottled clay horizon (MCH ). A selective sampling of
red [RD(a), RD(b), RD(c)] and white domains
[WD(a), WD(b), WD(c)] was made within the three
parts of the mottled clay horizon namely a, b, and c.
4) Iron crust (ICR) and loose nodular horizon (LNH).
Representative (about 2 kg) samples of both horizons
were collected. In the loose nodular horizon, the nodules
(NOD) and the yellow clayey matrix (MAT) were sep-
arated by sieving.
LABORATORY TECHNIQUES
Study of the Syenite Minerals and Their Weathering Products
Weathering petrography
The identification of the primary minerals and their weathering
products was done on ( I ) thin sections of rock and soil, (2) mineral
separates, derived m~neticaily and by the use of heavy liquids, and
(3) undisturbed soil volumes with optical microscopy and scanning
electron microscopy (STEREOSCAN 250 CAMBRIDGE coupled
with a PGT SYSTEM III Energy Dispersive Spectrometer). Back-
scattered electron imaging was also used.
Quantitative eIementa~analysis
Separated grains mounted in resin and polished were analyzed
with a CAMECA SX 50 for the accessory minerals (epidote, apatite,
sphene, atlanite) and selected secondary REE-Th-bearing minerals.
The experimental conditions are indicated in BRAUNet al. ( 1990).
The standards used were synthetic monominerals of inter-metallic
com~unds (Ge, Ru) for REEs (La, Ce, Nd, Sm, Gd) and oxide for
Th. The detection limit was approximately 500 *g/g in the best con-
ditions. For each mineral, point analyses and profiles were done. The
numerous analyses were statistically checked by principal component
analysis (PCA) in order ( 1) to remove the spurious analyses, and
(2) to determine inter-elemental correlations especially between the
elements constituting the &essory minerals and the secondary REE-
Th b-earing phases.
REE and Th anal.vsisin mineral separates
REE and Th contents of separates of alkaline feldspars (albite and
microcline), aegirine-augite, magnetite, apatite, epidote, allanite, ti-
tanite, and zircon were analyzed by isotope dilution mass spectrometry
(IDTIMS) (CAMECA 206TSN) following MICHARDet al. ( 1986)
and/or inductively coupled plasma mass spectrometry (ICPMS) fol-
lowing JARVIS( 1988). Particular attention was paid to the purity of
mineral separates. The mineral fractions were weighed with an ab-
solute precision of +-1 pg, and dissolved in teflon beakers with HNOr
HF-HCI. The precision for each REE is in the range of 0.1 -I% for
IDTIMS and about &5% for ICPMS. REE contents of zircon grains
have been determined by secondary ion mass spectrometry (SIMS)
(CAMECA IMS3F) at CRPG (Nancy). The precision is about
2 10% for each REE. The Th contents of two zircon separates have
4421
been determined by ICPMS &er the d~om~sition of the grains
with HF at 280°C in Teflon beakers.
Mass Balance CaleaIationsin the Whole Profile
Density measurements
The bulk densities were determined with a Go8uel* densimeter
for the freshest and weathered syenite with boulders weighing about
400 g, and by the cylinder method for the yellow and red saprolite.
Quantitative elemental analysis
AAer app~p~te crushing, pulve~~tion, and hom~eni~tion
procedures, each soil and rock sample was analyzed for major (Si,
Al, Fe, Mg, Ca, Na, K, Ti, P, Mn) and trace elements (REE, Zr) by
inductively coupled plasma atomic emission spectrometry (ICPAES).
The detection limit was about one to three times chondrite for the
REE. The errors ( f 1u) are about +5% for Zr and each REE, except
Lu ( + 15%). Gadolinium concentrations, inducing the positive Gd-
anomalies mentioned by BRAUN et al. (1990), but not discussed,
have been shown to be analytical artifacts. Because of their low con-
tents in the rocks, U ana Th were determined by ICPMS at IRSHP-
Nancy (VG@’ISOTOPE PLASMAQUAD, C. Rosin, analyst) and at
CRPG-Nancy (PERKIN-ELMER SCIEX, G. Mevelle and G. Gov-
indaraju, analysts). The BR (basalt) and DRN (diorite) international
rock standards were used. The samples were decomposed by fusion
with LiBq and dissolved in HNOl 1 N ( GOVINDARAJIJand MEV-
ELLE, 1987). Analytical uncertainties are less than 3%for U and 5%
for Th. The detection limit under the analytical conditions used was
0.5 ppm and 0.25 ppm for Th and U, respectively.
RESULTS
The Parent Rock: The Akongo Syenite
The syenite sample used as a geochemical reference in this
study was collected from the bottom flag. The hand specimens
of the Akongo pit syenite have a granular structure with a
slight mineral orientation defined by pyroxene crystals. The
texture is porphyroblastic with pyroxene and perthite blasts.
The major minerals are perthite (microcline and albite), ae-
girine-augite, actinolite, biotite, and magnetite. The accessory
minerals include &on, titanite, alla&e, epidote, and apatite
whose occurrence and aIteration features are described by
BRAUN et al. ( 1990). Based on color and magnetic suscep-
tibility, two populations of titanite crystals can be distin-
guished in grain size fractions. The most abundant is orange
yellow while the second, much more rare, is light yellow.
Fu~e~ore, EDIMO( 1985), who studied the parageneses
of the Akongo-Lolodorf syenitic axis, reported the presence
of rare thorite ( ThSi04) and monazite (LREEPO,+) crystals
in some samples of the Akongo syenite collected near the
studied pit. The occurrence of accessory quartz crystals is
also mentioned by BILONG( 1988) in the pit syenite.
Modal Analysis
Modal analysis of the syenite was based on point counts
of four thin sections totalizing about 40 cm2. A large number
of points {2~) were counted with an interactive video-
graphic analyzer ( LAPIQUEet al., 1988) COUQ~~~ with an op-
tical microscope to reduced uncertainties in the abundance
of the accessory minerals. Selected mineral density data
(DEER et al., 1985) were used to convert volume fractions
obtained from point counting into weight fractions taking
4422 J. J. Braun et al.

TABLE 1.Whole syenite ICPAES concentrations of major elements (in oxide wtl)
and ten REE, U, Th and Zr (in ppm) and modal analyses of the syenite minerals from
point counting (in volume and weight percent). Errors are calculated both from counting
statistics and from density uncertainties.
whole rock analysis (FSY) modal abundance
% ppm volume % weight %

SiO2 59.37 La 69.48 alkaline feldspars 64.3 r 0.2 60 +5

A1203 16.57 Ce 139.97 asglrlne-auglte 10.7 f 0.2 14 fl
Fe203 5.09 Nd 65.64 acllnollle 1.0 f 0.1 1.2 f0.1
Ma0 0.06 Sm 10.71 blotlte 1.0 to.1 1.1 zto.2
M@ 1.14 Eu 2.93 magnetite 1.2 *0.1 2.3 f 0.2
CPO 2.54 Gd 6.54 apatlte 0.80 i 0.1 0.9 * 0.1 0.94
Nn20 3.47 Dy 2.66 epldote 0.75 f. 0.05 0.9 * 0.1
K20 9.19 Er 1.13 allanlte 0.07 * 0.02 0.10 r 0.02
TiOZ 0.24 Yb 0.90 1ltanlte 0.10 k 0.02 0.13 + 0.03
PZOS 0.40 LU 0.13 zircon 0.01 r 0.01 0.02 * 0.01 0.04’
L.O.I. 0.92 ZREE 300.29

Total 96.99 U 5.5

Tb 3.1
Zr 169

* Apatite and zircon weight percent assume that all of the whole rock P is included
in apatite and Zr in zircon.

relative density errors of 5%. The volume percent and the
calculated weight percent modal abundances of the syenite
minerals are reported in Table 1. The whole syenite analysis
is also given. Although accessory mineral abundances ob-
tained from point counting are not entirely reliable ( GROMET
et al., 1983), this method was applied here because the cal-
culation of mineral weight fractions from the whole rock
quantitative analysis and the mineral compositions did not
give coherent values. This was due to the fact that the whole
syenite analysis reflects a slightly weathered rock in which
Na and Ca are already depleted. Moreover, apatite and zircon
abundances have also been calculated assuming all of the
whole rock P is included in apatite and Zr is in zircon. These
calculations may overestimate the amount of apatite and zir-
con in the rock. The results are reported in Table 1. For both
minerals, the data are similar indicating that the apatite and

TABLE 2. Average electron microprobe analyses (+ 1u) of selected accessory minerals.

apatite orange yallow light yallow epldote allanite allanite

tltanlte tltanlte
number of 1641 I651 [411 1211 [& r&
analyses

ws 42.05 f0.67 SiOz 29.16 f0.25 30.44 + 0.33 sioz 37.36 rt 0.67 33.43 f 2.17 30.65 * 0.37
CaO 57.16 f0.40 AlsO, 1.39 f0.13 1.12 zto.10 AW’a 20.73 f 0.37 16.65 f 2.34 12.66 f 0.46
Na,O 0.32 f0.04 FeO, 1.67 f0.14 1.22 1tO.16 FeOt i3.88 i 0.48 14.55 * 0.71 15.46 f 0.46
Ce#s 0.34 f0.11 CaO 26.06 f0.25 28.17 f 0.31 CaO 20.75 f 0.44 16.11 i 2.71 11.59 f 0.51
La205 0.10 f0.06 TIOz 35.29 f 0.34 37.23 f0.44 M&IO cdl 0.34 *0.21 0.96 * 0.21
F 2.14 f0.04 Las03 0.25 f0.12 < dl MnO 0.28 fo.lo 0.20 f0.12 0.41 f 0.18
Cl 0.05 f0.03 CeaOs 1.90 f0.14 0.45 f0.12 Ti02 c dl 0.24 to.14 0.66 +0.17
102.17 Nd203 1.02 f0.21 < dl La203 < dl 2.75 k 1.22 6.10 + 1.15
H,O’ [l.ll] [l.lS] C-w3 < dl 7.18 f3.40 12.19 + 0.30
-0.F 0.90 NdzO, < dl 2.73 -t 1.04 2.40 to.52
-O&I 0.01 HzO’ Il.751 [1.60] rl.481
0.91

total 101.26 total 97.87 99.79 total 94.77 95.78 94.56

number of ions on the basis of :

26(O) ZO(O,OH) 20(0,OH) 13(0,OH) 13( O.OH) 13(0,OH)

P 6.00 Sl 3.93 3.95 Sl 3.20 3.13 3.11

Al 0.08 0.05 Al
Ca 10.33
Na 0.05 Al 0.14 0.12 Al 2.10 i .a4 1.51
CO 0.02 Fe 0.19 0.13 Fe 0.66 1.14 1.31
La 0.01 T1 3.57 3.63 MS 0.05 0.15
Mn 0.02 0.02 0.04
F 1.14 Ca 3.76 3.92 Tl 0.02 0.05
Cl 0.01 La 0.01
Ca 0.09 0.02 Ce 1.91 1.61 1.26
Nd 0.05 La nd 0.09 0.23
Cs nd 0.25 0.45
OH’ 1.00 1.oo Nd nd 0.09 0.09

OH’ 1 .oo 1.00 1 .oo

(Le/Nd),h 2.2 to.7 5.2 f2.2

* Hz0 contents are estimated. tdl: under detection limit.

 Geochemistry of REEs and Th in a lateritic soil profile
zircon percentages are about 1 wt% and 0.02-0.04 wt%, re-
spectively.
Location of REEs and Thorium in the Parent Rock
In order to assess the contribution of each mineral to the
REE and Th budget in the bulk parent rock, point and bulk
analyses were made of the syenite minerals. Microprobe
analyses of the accessory minerals (apatite, light and orange
yellow titanite, allanite, epidote) are presented in Table 2.
The methods which were used for the REE analyses (IDTIMS,
ICPMS, SIMS) and the REE contents of mineral separates
(alkaline feldspars, aegirineaugite, magnetite, apatite, orange
yellow titanite, allanite, epidote, zircon) are reported in Table
3. The ICPMS Th contents of the minerals separates are also
mentioned. The REE and Th contents of actinolite and biotite
have not been analyzed because of the difficulties involved
in concentrating these minerals. The chondrite REE nor-
malized patterns of minerals and whole rock (FSY) are shown
in Fig. 2. These data show a wide range in concentration,
about lo5 for REEs and lo4 for Th, reflecting the strong
mineralogical control on the distribution of these elements
in the syenite.
Major Minerals
The perthite feldspar separate has REE and Th contents
much lower than those of the whole rock. The chondrite-
normalized REE pattern also shows a significant enrichment
in LREEs and a positive Eu-anomaly which is commonly
encountered in perthite (HENDERSON, 1984). The inclusion-
free magnetite separate has REE contents lower than those
of the syenite and shows slight enrichment in LREEs. Du-
plicate analyses of clinopyroxene separates weighing about
2.5 mg do not have similar REE concentrations. The REE
and Th contents of the separates are either one or two times
those of the whole rock and the patterns show an enrichment
in LREEs. The overestimation of the REE concentrations of
the aegirine-augite is probably due to the presence of LREE-
rich inclusions, such as titanite and epidote, frequently ob-
served within the pyroxene crystals.
Accessory Minerals
Apatite and titanite
The apatite is a fltior-apatite showing a slight substitution
ofCa’+ by La3+, Ce3+, and Na+ . The orange yellow titanite
crystals are richer in Al, Fe, La, Ce, and Nd than the light
yellow crystals. The Gd and Th concentrations are beneath
the detection limit of the electron microprobe. Step profiles
in some apatite and titanite crystals reveal a heterogenous
distribution of the LREEs (La, Ce, Nd). The two apatite and
two orange yellow titanite separates are free of inclusions.
Both ICPMS or IDTIMS REE data are similar. Moreover
the La, Ce, and Nd contents are consistent with the average
microprobe concentrations. The apatite pattern shows a
LREE enrichment [(La/Yb)=,, = 601 whereas the titanite
pattern has a MREE (Nd, Sm) enrichment and a marked
depletion in La. The apatite and orange yellow titanite are
the most REE-rich phases in the syenite. The REE contents
4423
for apatite and titanite are twenty and one hundred times
those of the syenite, respectively.
Epidote and allanite
Compared to allanite, epidote has higher Si, Al, and Ca
and lower Fe concentrations. An inclusion free epidote sep-
arate has a LREE enrichment [( La/Yb),h = 671. The REE
and Th contents are two and eight times those of the syenite,
respectively. Allanite is the most LREE and Th rich phase
of the rock. The (La/Yb),,, ratio is higher than 2000, dem-
onstrating the extreme LREE enrichment. The Th, Sm, and
Gd concentrations are beneath the detection limit of the mi-
croprobe. The allanite analyses have low totals because Pr2O3
and Fe203 are not determined. Step-profile and point micro-
probe analyses on zoned allanite crystals allowed the complex
distribution of elements, especially of the lanthanides, to be
distinguished. Chemically different zones have been identi-
fied: the first zones (Z 1) present increasing Ce, La, Nd con-
tents with distance in the crystal profile, whereas in the second
zones (Z2), the Nd contents decrease while La and Ce con-
tents continue to increase. The average chemical composi-
tions of allanite for the zones Zl and 22 and the (La/Nd),,
ratio, which is used to quantify the LREE fractionation, are
presented in Table 2. The (La/Nd),h ratio indicates that the
zones 22 are more fractionated than the zones Z 1. The precise
relation between Fe and the other elements is not completely
determined because the microprobe does not measure the
Fe’+/ Fe3+ ratio. The separated inclusion free euhedral allanite
crystals are strongly zoned in concentration. The ICPMS La,
Ce, and Nd contents are lower than the electron microprobe
data. It is difficult to establish a multiplying factor between
the microprobe and ICPMS analyses due to the complex
substitution of the LREEs in the allanite crystals.
Zircon
Except for the heaviest REEs (Dy to Lu) zircon has REE
contents much lower than the whole rock while the Th con-
tent are about thirty times those of the syenite. The ion mi-
croprobe analyses of the zircon rim and core reflect the het-
erogeneous distribution of REEs in the crystals. The chondrite
normalized REE patterns show extreme enrichment in HREE
and positive Ce-anomalies. Such Ce-anomalies have been
reported by MURALI et al. ( 1983) and HINTON and UPTON
( I991) for zircon.
Mass Balance for the REEs and Thorium
in the Lateritic Profile
Location of REEs and Thorium in the saprolite
A petrographical and mineralogical study of the weathering
products was conducted in order to understand the mobili-
zation and fractionation processes of the elements with par-
ticular emphasis on the saprolite. The evolution of major
and accessory minerals during weathering is described in
BRAUN et al. ( 1990). However, further observations have
been made concerning the weathering of the accessory min-
erals (zircon, apatite, epidote, allanite, titanite) and the oc-
currence and chemistry of the secondary REE-Th-bearing
phases ( florencite, rhabdophane, cerianite).
4424 J. J. Braun et al.

TABLE 3. REE and Th concentrations (in ppm) of mineral separates of the Akongo syenite as determined by different analytical
techniques. Average microprobe analyses are in oxide wtl. The syenite REE concentrations (FSY) are indicated.

I APATITE I TJTANITE 1 EPIDOTE 1 ALLANITE I

IDTI ICPMS microprobe JDTJ JCPMS microprobe microprobe JDTJMS ICPMS microprobe microprobe
MS Illl~IySlS' MS MlllySiS* PhlG3lYSiS' analysis* anPlySiS*

orange orrqge orange yellow light yellow Zl zones 22 ZO”fYS

yellow yellow titanite titanlIe 27 anrlvses 86 ~nnlvses
titan. titan. (+ Jai (% loi

LO 1659 1471 0.09 f0.07 3144 2590 0.22 +0.11 <dl 528 26265 2.3 f 1.0 5.2 il.0
Ce 4060 4158 0.30 i 0.10 11650 13337 1.62 f0.12 0.39 fO.ll 1080 37743 6.1 f 2.9 10.4 f 0.2
Nd 2525 2079 nd 7850 5736 0.87 f0.19 cdl 495 10506 2.3 f0.9 2.1 f 0.4
Sm 395 367 nd 1395 1109 nd nd 76 584 < dl <dl
EU 66 64 nd 330 225 nd nd 26 107 nd nd
Gd 230 295 nd 800 772 <dl <dl 47 584 <dl <dl
J'Y 86 89 nd 362 275 nd nd 19 58 nd nd
Er 28 nd nd 117 nd nd nd 6.3 39 nd nd
Yb 19 nd nd 89 nd nd nd 5.3 <lO nd nd

ZREE 9088 8523 0.39 25737 24044 2.71 0.39 2263 75886 10.7 17.7
(La/Yb),,, 58.3 23.8 - 67.5 >moo -
EulEu* 0.9 0.7 - 1.0 0.8 1.4 0.6
ce/ce* 1.0 1.2 - 1.3 1.9 1.0 0.9 1.3 1.3

Th 35 226 24 661

nd: not determined.

Zircon crystals (Fig. 3a) which came directly in contact
with corrosive soil solutions have coJ-rosion features as shown
by grains found in the white clayey seams of the saprolite
(Fig. 3b). However, some crystals preserve their original
morphology throughout the whole profile when they are
embedded in clayey ferruginous concretions.
Florencite [ LREEAls( P04)20H6] has been clearly iden-
tified by X-ray diffraction in an aggregate separate obtained
by heavy liquid and magnetic separation from the weathered
syenite. Zircon and titanite peaks have also been identified
in the mixture. The clay material observed by SEM and an-
alyzed with EDS (Fig. 3d) does not show X-ray signature.
The florencite donuts (from 1 to 5 pm in diameter) grew on
the residual walls and in the dissolution cavities of weathered
apatite (Fig. 3c) and allanite crystals. Florencite was also
found admixed with anatase (Ti02) in the weathering prod-
ucts of titanite. Quantitative point analyses and step profiles
have been done within the most homogeneous zones and the
REEs richest donuts of thirteen selected aggregates similar
to that presented in Fig. 3d. The analyzed donuts were pre-
viously identified with the SEM using backscattered electron
mode. The average analyses and the standard deviation of
three representative donut aggregates are reported in Table
4. An analysis from the Si-Al-Fe matrix admixed with the
donuts and from a 2 pm rhabdophane crystal found in a
dissolution cavity of an apatite grain are also given. Samarium
and sulfur have been analyzed but they are generally present
in quantities too small to be detected with the electron mi-
croprobe, except for Sm in rhabdophane. The relative errors,
calculated for each analyzed element, are indicated in Table
5. All the analyses of donuts have low totals (73-86 wt%),
indicating porous and/or hydrated materials. Significant
variations in element concentrations of donuts are found both
between different aggregates and within single aggregates. The
one hundred ninety one electron probe analyses conducted
on the donuts and the associated matrices suggest that the
donuts are complex assemblages of weathering products
composed of a mixture of Fe, Ti, Si oxides and aluminous
phosphates of LREEs, Ca, Sr, and Ba. However, LREEs are
not strongly correlated (r = 0.5) with P and Al, suggesting
that they could also be incorporated in other phases. Thorium
seems to be correlated with Fe, Ti, and Si, but this correlation
is not well defined because Th concentrations are often below
the detection limit of the electron microprobe. Cations that
are able to substitute for LREEs in the florencite lattice, such
as Sr, Ca, and most importantly Ba, are always abundant
(Fig. 4). The florencite fraction of the donuts ranges from
50 to 70%, calculated assuming the idealized formula (LREE,
Ba, Sr, Ca)AlJ( PO,h. OH6 and assuming that all P is in the
aluminous phosphate.
The fractionation of Ce in aluminous phosphates is com-
plex. Florencite- ( La) with negative Ce-anomaly ( Ce /Ce *
= 0.4), florencite-( Ce) with slight negative Ce-anomaly (Ce/
Ce* x 0.7) and florencite-(Ce) without Ce-anomaly can
coexist in the weathered syenite. The most abundant is the
florencite-( Ce) with Ce/Ce* ofabout 0.7. The ICPMS chon-
d&e-normalized REE pattern of an aggregate separate is
compared to those of the REE-bearing accessory minerals in
Fig. 5. Compared to allanite, the aggregate has a flatter REE
pattern and a slightly negative Ce-anomaly. The weathering
products are strongly enriched in LREEs compared to apatite
and titanite. The ICPMS Th concentration of the aggregate
separate is 2000 ppm. It is enriched in Th compared to the
Th-richest accessory minerals from which it developed. The
analyzed rhabdophane crystal located in an apatite dissolution
cavity presents both an enrichment in LREEs [(La/Nd),,,
= 3.31 and a slight Ce-anomaly (Ce/Ce* = 0.7). The Si,
Al, and Fe contents are probably due to nearby clays rather
than the rhabdophane itself.
In the other parts of the saprolite the donuts appear either
isolated in the sandy matrix or as chains at the boundary
between porous (red sandy saprolite) and compact domains
(white clayey seams). Cerianite ( CeOz), showing a possible
substitution of Ce by Ti (Fig. 6), has been identified in sig-
nificant amounts within the white clayey seams of the middle
part of the saprolite ( BRAUN et al., 1990).
 Geochemistry of REEs and Th in a lateritic soil profile 4425

Table 3. (Continued)

ZIRCON ALKALINE WGIRINE MAGNETITE SYENITE

FELDSPARS -AUGITE WY)
SIMS SIMS ICPMS ICPMS IDTIMS

rim core
1 att8lYsir 5 atta1vses

La 0 0.1 6 209 20 69.46

Ce 6.0 22.4 f2.1 9 410 49.6 139.97
Nd 0.6 1.0 *0.2 5 170 16.4 65.64
Sm nd nd 2.5 23.9 2.9 10.71
EU 0.9 0.6 f0.2 1.3 5.9 1.2 2.93
Cd 0.6 3.4 f1.9 0.3 14.5 1.9 6.54
DY 3.1 7.2 f3.4 < 0.06 6.97 1.1 2.66
Er 9.1 13.9 f6.6 < 0.02 2.6 0.5 1.13
Yb 17.5 23.6 f14.3 < 0.02 3.12 0.5 0.9

ZREE 40 72.2 24.3 646 96 300.29

(LaIYb),k - >200 30.4 27.52 52
EttlEtt* 11.3 3.9 2.6 1.0 1.77 1.0
CelCe* 36.7 39.9 0.6 1.22 1.0

Th 60 (ICPMS) 0.11 3 nd 3.1

nd: not determined

Mass Balance Calculations Using Thorium as the Invariant
in the Whole Profile
The concentrations of major (Si, Al, Fe, Mn, Mg, Ca, Na,
K, Mn, Ti, P) and selected trace elements (REE, U, Th, Zr)
from the different zones of the profile used for the calculations
are reported in Table 6.
IO’
Assuming that their distribution is homogeneous in the
parent syenite, Ti, Zr, and Th can be used as immobile ele-
ments for mass balance calculations in the supergene envi-
ronment. The behavior ofthese elements has been compared
to select the best among them with isovolume mass balance
calculations ( MILLOT and BONIFAS, 1955) in the weathered
syenite and the yellow and red saprolite where the original
structure and texture are preserved. This is mainly supported
by petrographical observations showing that the well-pre-
served K-feldspar crystals constitute the framework of the
saprolite zones ( BILONG, 1988). The isovolume mass balance
equation can be written as follows:

(1)
lo5

e.!Jr
- 1
c es* PS
% change = A- I -100,
[C Ppr
10’

where C& and Ce,prare the element (e) concentrations in the

W soil sample and the parent rock, respectively, and where pr
: lo3 and ppr are the bulk densities. The variations (in percent) as
a function of the gradual weathering of the syenite are illus-
:
trated in Fig. 7. There is Ti and Zr loss in the yellow saprolite
i!i
_ lo2 whereas thorium shows neither enrichment nor significant
a
depletion in the different saprolite zones. Thorium seems to
z
be the least mobile element in the saprolite and, hence, has
z 10’ been used for the mass balance calculations for the whole
s
profile.
In the other parts of the profile (mottled clay horizon, iron
10”
crust, loose nodular horizon) the original structure and tex-
ture of the syenite is not preserved, so mass balance calcu-
lations require the use of an invariant element. The relative
10”
mobilities of the major and trace elements in the soil are
shown in Table 7. The percentage increase or decrease of
10-z
!N.
,
):
any element in a soil -sample relative to fresh parent rock is

(G,s/Ci,s)
Er Vb calculated according to NESBITT ( 1979
FIG. 2. Chondrite normalized REE patterns for eight mineral phases
in the Akongo syenite. The “aegyrine-a&e” pattern represents a
global analysis including the inclusions. Zircon rim and core (average
=[fCe,pr,Ci,pr)
%change - 11-1W (2)
of five analyses) patterns are shown. The whole rock REE pattern is
also shown. See Table 3 for data. Data measured by ICPMS, IDTIMS, where C’,, and Ce.prare the same parameters as in Eq. 1 and
and SIMS. Ci., and Ci,p, are the concentrations of the immobile element
4426 J. J. Braun et al.

FIG. 3. (a) Unweathered zircon grain from the freshest syenite (SEM-b&scattered electron mode). (b) Partially
dissolved zircon grain from a white cIayey seams of the saprolite (SEM-backscattered electron mode), (c) Detail view
of residual walls of an apatite crystal on which tlorencite donuts (Fl) have grown. (d) Polish section of an aggregate
cf florencite donuts (ff ). The donuts are mixed with an amorphous AI-Si phase (AS) (SEM-scatty electron
mode).

( I ) in the soil sample and the parent rock, respectively. Dia-
grams in which the percent change of the REE are plotted
vs. atomic number are presented in Fig. 8. The mass balance
has not been calculated for the white clayey seams due to
their origin. It is important to note that the Th content of
these zones is less than that of the parent material. All ele-
ments which are present in these zones may be considered
to be accumulated. From Tables 6 and 7, the following may
be concluded.
1) Zr shows only small losses in the saprolite and iron-rich
horizons and Ti shows significant redistribution within
the whole profile, especially in the white seams where it
is most strongly concentrated.
2) Except for Fe, the major elements are depleted in the
upper horizons (ICR, LNH, and the top of the MCH).
In the zones which are periodically exposed to the water
table ( WSY, YSAP, RSAP, red and white domains of the
bottom of the MCH), alkalines, alkaline earths, and Si

TABLE4. Avenge microprobe analyses and standard deviation (+ I (I) for the donuts
of 13 selected aggregates. The number of analyses for each aggregate is indicated. An
analysis of the Si-Al-Fe-Ti mixing phase and an analysis of a rhabdophane crystal are
also indicated. Analytical erron are indicated. (i..a/Nd)ti and Ce/Ce* have been calculated.
Florenclte donut aggrogetes matrix rhsbdophane
Number of 1401 [ill r151 [II 111

p205 16.6 f 2.0 18.1 f 2.1 13.6 k 1.0 0.3 ?:0.1 29.0 TO.6
A1203 28.5 f 4.9 29.3 f 2.4 21.0 f 1.1 18.7 t 0.4 r.2 +0.1
FeOt 10.1 f 8.1 7.5 f 4.1 20.4 t 3.5 21.1 + 1.0 0.8 i0.2
TlO2 1.9 _+1.6 1.2 + t.2 2.2 f 0.5 0.5 t 0.3 <dl
ThO2 0.3 f 0.2 0.1 + 0.1 0.3 + 0.2 <dl <dl
sioz 2.2 f2.0 3.3 k3.7 7.3 + 3.4 45.3 i:0.5 0.2 4 0.1
cao 0.9 f 0.2 1.1 c 0.1 0.7 * 0.1 cdl 3.0 f0.2
SaO 3.1 kO.9 3.9 f 1.4 2.3 f 1.1 cdl 0.4 k 0.1
SrO 1.5 io.5 2.0 f 0.3 0.8 f 0.3 cdl <dl
La203 4.9 f 1.6 3.8 f 1.1 5.5 * 1.0 cdl 19.0 f 0.8
Ce203 5.3 k1.2 6.5 + 1.2 3.9 f 1.0 cdl 22.2 il.3
Nd203 2.5 IO.4 2.6 f 0.6 3.4 i 1.4 edi 11.1 +f.$
Sm203 cdl cdl sdl <dl 1,o +0.5

Total 77.0 79.5 81.3 85.9 85.9

Ce/Ce* 0.69 f 0.17 0.96 f 0.26 0.41 k 0.08 - 0.66

(Lalf'Wc h 3.98 C 1.59 2.71 kO.86 3.67 If: ‘I.95 - 3.32
 Geochemistry of REEs and Th in a lateritic soil profile 4427

TABLE5. Approximate relative er-

rors (in %) for the analyzed element6
in the donuts for different concentra-
tion levels.
microprobe analyses
of florenclte donuts
level 5000 ppm 1% 5% 10%

__ _
Ca 10 - -
Sr 17 -
Ba - 10 -
1, . 10 3
2 - lb : La Ce
_ _
Tl :; _ _
are removed. Iron is redistributed over short distances,
leading to the presence of Fe-poor and Fe-rich domains
side by side within the mottled clay horizon. Iron is leached
in the saprolite. Aluminium is relatively stable and is ac-
cumulated at the bottom of the profile. In the white seams,
Si and Al are concentrated.
3) Throughout the profile, U is strongly depleted, behaving
much like the most mobile alkalines and alkaline earths
(Ca, Mg; Na). The REE have variable behaviors within
the different zones of the profile. Most REEs are leached
in the Fe-rich upper horizons (loose nodular horizon, iron
crust, and the top of the mottled clay horizon, Fig. 8a).
Where the water table moves, the REEs are concentrated
in the clayey zones in which the soil solutions have a
longer residence time during water table discharge. These
zones are the white domains of the mottled clay horizon
(Fig. 8b) and the white clayey seams of the middle part
of the saprolite in which Ce is strongly concentrated. The
REE behavior in the isovolume weathering zones is char-
acterized by the juxtaposition of leached and accumulation
zones. The leached zones are the yellow and red saprolite
(Fig. 8c) and also the red domains of the mottled clay
horizon bottom (Fig. 8b). The accumulation zone is the
weathered syenite (Fig. 8c) in which the LREEs are ac-
Ba
._
Nd SmEuGd Dy Er Yb
FIG. 5. Chondrite normalized REE patterns for the main primary
bearers (allanite, 0, apatite, 0, titanite, A, and the donut aggregate
separate (0) of which the major part is composed of florencite-(Ce).
cumulated whereas the HREEs are partially leached away.
Ce tends to be enriched compared to the other REEs in
the yellow and red saprolite.
DISCUSSION
Distribution of Thorium and REEs in the Syenite:
The influence of the Accessory Minerals
The fractional contribution of each mineral to the whole
rock REE and Th contents of the syenite is shown in Fig. 9.
Because of the uncertainties in the REE concentrations of
the aegirine-augite, they have not been taken into account
in these calculations. The SIMS average REE contents of
core zircon were used for these calculations. The ICPMS REE
and Th contents of the allanite separate are considered to be
representative despite the heterogeneous distribution of ele-
ments in this mineral.
It is apparent that accessory minerals control the REE and
Th concentrations in the Akongo syenite. These minerals
are, in decreasing order of importance: apatite, titanite, al-
lanite, and epidote. This accessory phase control on the lan-
thanide and actinide distribution is common within most of
the granitoids ( FOURCADEand ALLEGRE, 1981; PAGEL, 1982;
GROMET and SILVER, 1983). In the Akongo syenite, apatite
and titanite are of dominant importance in the middle and
heavy REEs, whereas allanite is important for the lightest

0
s o”0 O
z ,_ 0

E
l-
0 O
I

y = 0.02 + 0.06x R I 0.94

. ’ o . 8 .
10 20 30 40
Ce02 (wt%)
La+Ce+Nd sr+ca
FIG. 6. Correlation between TiOz and Ce02 in the cerianite ac-
RG. 4. Electron microprobe analyses for Sr, Ra, Ca, Ce, La and cumulation zone of the white clayey seams of the middle part of the
Nd from aggregated donuts of the weathered syenite. saprolite (microprobe analyses).
 TABLE 6. ICPAES concentrations of major elements (in oxide wt8) ten REE and Zr fin ppm) and ICPMS concentrations of U and Th (in ppm). Three replicate
analyses (2 1u). The characteristic ratios are calculated as follows for the REEs:

(La/Ybb = (La/La&(YW’b~ ): (La/W%, = (La/La,)/(WYb,,)

Ce/Ce* = Ce-anomaly = (Ce/Ce,,,)/(La/L&,h)2’3(Nd/Nd,,,)”3
ch: chondrite and sy: syenite (parent rock).

LOOSE
SANDY SAPROLITE WHITE CLAYEY MOTTLED CLAY HORIZON IRON NODULAR
SEAMS CRUST HORIZON
FSY WSY YSAP RSAP WCS1 WCS2 WCS3 RDa WDa RDL WDb RDc WDc ICR MAT NOD

SiO2 59.37 58.95 54.92 50.34 46.52 45.95 45.21 44.67 44.18 45.82 44.32 43.92 46.79 36.35 45.82 17.23
16.57 17.95 21.10 22.73 32.oo 33.28 33.59 22.23 33.65 22.33 34.96 24.32 32.29 24.35 22.91 19.03
A’2O3
5.09 5.34 5.92 a.89 1.62 1.92 1.45 14.75 3.47 13.35 2.24 13.89 2.95 22.17 13.85 46.45
Fe203
MnO 0.06 0.02 < dl <dl < dl < dl IC:
dl < dl < dl 0.01 < dl 0.01 cdl < dl 0.02 0.03
MgO 1.14 0.48 0.12 0.10 0.07 0.10 o.o4 0.07 o.io 0.04 0.05 0.04 0.08 0.11 0.14 0.07
CaO 2.54 0.60 0.03 0.05 0.04 o.o6 0.06 0.03 0.05 0.01 0.01 < dl < dl 0.02 0.02 n.d.
Na20 3.47 2.50 0.44 0.29 0.10 0.06 0.07 0.22 0.03 0.24 0.01 0.17 0.05 0.04 0.08 n.d.
9.19 10.92 11.41 8.99 3.07 2.37 2.W 7.21 1.11 7.53 0.76 5.82 2.00 1.68 2.49 0.11
K2*
TiO2 0.24 0.26 0.29 0.45 0.20 0.34 0.17 0.58 0.53 0.64 0.34 0.56 0.71 0.76 1.06 0.48

P2Os 0.40 0.26 0.26 0.26 0.22 0.2O 0.28 0.30 0.32 0.30 0.32 0.30 0.20 0.28 0.25 0.40
L.O.I. 0.92 1.61 4.57 6.96 16.02 15.39 17.15 9.04 16.23 a.78 16.70 10.06 14.54 13.93 12.95 14.62

Totsi 98.99 96.99 99.06 99.06 99.92 99.67 100.02 99.10 99.67 99.05 99.71 99.11 99.61 99.69 99.59 98.42

La 69.48 115.15 e4.74 100.24 47.16 49.83 69.36 521.56 154.45 55.85 177.27 64.90 70.70 83.14 67.86 52.26
ce 139.97 234.81 190.14 239.50 715.64 1395.34 2355.79 157.00 318.84 123.20 345.43 127.21 132.97 145.89 123.19 95.46
Nd 65.&Q 96.91 67.93 al.32 33.15 41.14 70.94 48.&l 156.54 50.71 162.36 64.71 51.54 51.80 44.07 31.25
Sm 10.71 14.01 10.24 12.12 4.51 6.07 11.01 7.95 25.30 a.21 25.99 9.07 8.41 8.50 6.95 5.51
EU 2.93 3.39 2.34 2.67 1.02 1.54 3.013 1.91 8.53 2.01 6.38 2.24 2.02 1.99 1.63 1.26
Gd 6.54 7.34 a.55 5.90 (5.37) (9.aa) (19.88) 4.44 16.58 4.62 16.08 5.29 5.27 5.41 4.43 3.87
DY 2.66 2.48 1.93 2.02 0.82 1.42 2.72 1.94 8.07 1.77 7.56 2.09 2.43 2.45 2.48 I.92
Er 1.13 0.94 0.74 0.77 0.39 0.56 0.97 0.81 2.90 0.75 2.70 0.87 1.06 1.22 1.19 0.89
Yb 0.90 0.63 0.42 0.51 0.27 0.43 0.61 0.62 1.69 0.52 1.49 0.57 0.76 0.88 1.11 0.70
LU 0.13 0.11 0.07 0.11 0.07 0.13 0.27 0.13 0.22 0.10 0.17 0.11 0.15 0.18 0.17 0.17

XREE 300.29 475.77 373.10 445.16 808.40 1506.34 3034.61 276.20 691.22 247.74 745.43 267.05 275.31 301.46 253.08 193.29

(LalYb),h 52 123 136 133 118 78 77 57 62 72 80 77 63 64 41 50

(L*lYb& 1.00 2.37 2.61 2.55 2.28 1.50 1.47 1.10 1.18 1.39 1.54 1.47 1.21 1.22 0.79 0.97
ceJce* 0.98 1.03 1.21 1.22 8.16 14.27 19.53 1.46 0.98 1.09 0.96 0.99 1.00 0.98 1.00 1.04

U 5.5O?0.09 2.35t 0.06' 1.08f0.05' 0.92+I0.02 0.3 0.5 0.3 0.7 1.0 0.4 1.1 0.9 1.0 21 2.7 3.1
Th 3.11f 0.19" 3.65c 0.03' 5.05i 0.11' 5.76t 0.32 21 29 2.6 6.7 72 4.7 5.5 5.8 5.2 13.3 15.2 20.9
UiTh 1.8 0.6 0.2 0.2 0.1 0.2 0.1 0.1 0.1 0.1 02 0.1 02 0.2 02 0.1

Zr 169 211 178 259 79 110 125 344204 357 118 309 270 305 685 315
 Geochemistry of REEs and Th in a lateritic soil profile 4429

100 and 50% of the Th. The REE and Th contribution of zircon
is extremely low ( <O. 1%) even for the heaviest REE which
Ill 50 is due to both the low volume fraction and low REE and Th
(3 contents. Concerning the major phases, perthitic feldspars
z 0 provide about 5% of the LREEs, except for Eu (35%), and
3 3% of the Th. As for magnetite, its, contribution is less than
g-50 1%. The REE and Th contents of the reconstructed rock are
lower than those of the whole rock. This could be due to: ( 1)
-1001 ’ I the lack of reliable data for aegirine-augite, actinolite, and
FSY WSY YSAP RSAP biotite, (2) nonrepresentative mineraL separates, (3) the
““;,~;;“’ (2,75iO.O5)(2.62~0.05)(1.4~0.1) (1.6kO.l) complex zoning in allanite, and (4) either HREE or LOPE
and Th-bearing minerals (e.g., xenotime, monazite, thorite)
INCREASING DEGREE *
OF WEATHERING which were not analyzed because of their low abundance
( ~0.0 1%) . Considering the distribution coeficients of REE
FIG. 7. Percentage change of Ti, Zr, and Th with relation to the
for the clinopyroxene (HENDERSON, 1984), the aegirine-au-
freshest syenite. The calculations are based on equal volumes of the
saprolite zones. Bulk densities of syenite, weathered syenite, and yel- gite ( 14 wt% of the whole rock) may account for about IO-
low and red saproiite are indicated. The shaded zone (&2O%) rep t 5% of the lightest REE, 30-40% of the intermediate REEs,
resents the range in which an element may be considered as immobile and 30% of the heaviest REE. On the other hand, considering
taking into account the analytical errors. its ICPMS Th content, the aegirine-augite provides a maxi-
mum of 14% of this element. The clinopyroxene may account
REEs and Th. Similar results for a granodiorite have previ- for the lack of REEs but not for Th for which about 40%
ousIy been reported ( GROMET and SILVER, 1983 ). These remains unexplained. According to MARIANO ( 1989), only
accessory phases account for about 70% of the lightest REEs, 4 - 10-3 wt% of xenotime would he sufficient to fill the de-
60% of the intermediate REEs, 40% of the heaviest REEs, pletion of both heaviest REE and Th. On the other hand,

TABLE7. Comparative mobility of the major elements, REEs, U, and Zr in the profile zones. Calculations have been made using Th as an
“invariant” element,

LOSSES

low low I
average high
-40% f
0% I > 100%
0%
+lOO%

LOOSE Fe

NODULAR
HORIZON Ti,Zr

Ti
IRON CRUST F8
REE,U

top Na,Ca,Mg Si,P,K Al Fe,Ti

zone c U REE Zr
RD *_--*--_*______“___ --______ -________ ________
MOTTLED bottom NaCa,Mg Si.P,K AI F6,Ti
REE Zr
CLAY zones a & b U

top Na,Ca.Mg Si,Fe,P

HORIZON tone c U REE,Zr Ti

WD .----------________ --______ .-___-_--

bottom NaSa.Mg Si,Fe,P

AI,Ti.REE
U Zr
zones a 81 b

RSAP Na,Ca,Mg Si,P.K Al,Fe Ti

I U I HREE LREE.Zr

Na,Ca.Mg Si,P AI,Fe.K.Ti

SAPROLITE YSAP U
I I HREE,Zr LREE

WSY I Ca
I f&l
U
Si,P,Fe,Na
AI,Ti,Zr.HREE
K
LREE
4430 J. J. Braun et al.
la)
-20
$ -40
9 The 50% of the Th which is released during the breakdown
0 -60
-60
(C)
-100
FIG. 8. Percentagechange ofREEs is shown relative to the immobile
element Th for the different soil zones: (a) loose nodular horizon
(nodule (NOD) and matrix (MAT)), iron crust (ICR), and top of
the mottled clay horizon ( WDc and RDc); (b) bottom of the mottled
clay horizon ( WDa, WDb, RDa, RDb); (c) weathered syenite (WSY)
and yellow and red saproiite (YSAP, RSAP).
4 - 10e4 wt% of pure thorite is sufficient to explain the whole
rock Th content.
Behavior of Thorium and ~ompari~n with Other
Immobile Elements
In the saprolite, the comparison between the behavior of
Th, Zr, and Ti has shown that Th is the least mobile element
(Fig. 8). Zirconium mobility is reflected by the petrographical
obviations of corrosion of zircons in the saprolite and the
other horizons. Despite the well-known resistance of zircon,
which is the main Zr-bearer in the granitoids, to weathering,
the corrosion of zircons has been frequently observed in iat-
e&es ( MILNES and FITZPATRICK, 1989). The metamictiza-
tion process may enhance the solubility of this mineral and
con~uently the release of Zr. Titanium mobility is indicated
by the presence of Ti in supergene cerianite in the white
clayey seams. The strong positive correlation between Ce and
Ti suggests that Ti is in substitution in cerianite. However,
the ionic radius of Ti (0.6 1 A, coordination number 6) is
too small compared to that of Ce (0.97 A, coordination
number 8) for such a su~titution. On the other hand,
GARDNER f 1980) has also shown the mobility of Ti during
weathering using isovolumetric mass balance calculation.
Mineralogical investigations of Th are difficult because of
its low abundance in both the syenite and accessory minerals.
of the accessory minerals may certainly be imm~iately re-
precipitated in situ. The precipitation of tiny crystals of sec-
ondary thorianite may be possible when the donuts are
formed. According to the principal component analysis, tho-
rium is apparently not included in the aluminous phosphates.
It could be precipitated as an oxide mixed with the Al-Si-Fe-
Ti amorphous or poorly crystallized phase. Thorianite is also
present as a 10 pm length crystal with corroded edges in the
weathered syenite ( BRAUN et al., 1990). In order to explain
this, some assumptions are necessary. In plutonic rocks, pri-
mary thorianite generally appears in strongly silica-under-
saturated rocks such as pyroxenite ( MOINE et al., 198s). Ex-
perimental studies on the ThO&JO&SiO~ system (SUMMON
and ROY, 196 1) show that thorianite only exists when quartz
is totally absent. Even when a very small amount of quartz
is present, the mineral which crystallizes is thorite ( ThSi04)
(CUNEY and FRIEDRICH, 1987). The presence of primary
quartz in the Akongo syenite has been observed by BILONG
( 1988 ) and the corroded edges of the tho~anite crystal may
indicate that this crystal is not of primary origin. Such cor-
rosion could result from the weathering of a thorite crystal
with leaching of the silica and the in situ precipitation of
ThOz. The low Th content of the syenite (3 ppm) suggests
that it was fortunate to observe even a single weathered crystal.
Throu~out the profile, Th is considered as the least mobile
element. By definition, Th is assumed to be unaffected by
redistribution processes. However, the mechanical transfer
of Th in soil solutions in suspended form can not be excluded
in the important leaching zone which is the loose nodular
horizon. Furthermore, Tb mass balance calculations are use-
ful because REEs and the majority of Th in the syenite are
contained in the same accessory minerals. Thus, Th can be
used as an accurate internal standard for the study of the
redistribution of the REEs.
Behavior of REEs in the Akongo Lateritic Profile
The seasonal fluctuation of the water table induces the
fractionation and leaching of the REEs in the saprolite. The
flooding of the saprolite leads to the breakdown of primary
REE-bearing phases and the release of REEs as trivalent cat-
ions. At this stage, REEs, especialiy LREEs, may be ( 1) in-
corporated in secondary REE-bearing phases (phosphates)
and ( 2) adsorbed onto clays (halloysite and g&hite). If we
refer to the REE concentrations measured in the water of the
marsh located between the syenitic Akongo hills, the soil so-
lutions in contact with the solid phase should contain a small
amount of soluble REEs (XREE w l-10 pg*l-‘) (BRAUN
et al., 1990). The marsh water floods a syenite bedrock. The
same weathering processes governing the REE in solution as
those encountered in the bottom profile may be supposed.
Moreover, the marsh water is enriched in HREEs compared
to the syenite due to the higher stability of HREE complexes
 Geochemistry of REEs and Th in a lateritic soil profile 4431

+ reconetn~eted rock

X alkallna
feldspars

* magnstfte

9 apatfts

f2 tltanlte

A epkfote

0 alianfte

,,*
La Ce Pr NdPmSmEuQdTb DyHo ErTmYbLuTh

FIG. 9. Fmc nal contribution of each mineral to the whole rock REE and Th contents of the syenite. A composite
reconstructed ck, calculated from the sum of the mineral contributions, is also plotted.

compared to those of LREEs. SMEDLEY ( 199 1), who studied
shallow groundwaters from the granitic Cammenellis area
( SW England), found higher REE contents in groundwaters
of pH < 6. Assuming that the pH of the water table is about
6, the soluble REE should be present mainly as free ions or
sulfate complexes after the models from TURNER et al. ( 198 1)
and WOOD ( 1990). However, a part of the HREE may exist
as carbonate complexes.
The rise and fall of the water table induce ( 1) contrasting
dynamics of the soil solutions in the sandy saprolite and in
the white clayey seams and (2) the return of oxidizing con-
ditions. A part of the REEs are leached away from this sap-
rolite located at the hill top.
The mineralogical investigation of the saprolite suggests
that phosphates play a major role in the REE trapping. The
aggregates of florencite donuts and rhabdophane crystals were
selected from the basal weathered syenite. C&mite was found
in the clayey Seams of the middle saprolite. Both domains
are accumulation zones. In the weathered syenite (WSY),
all the LREEs were concentrated, whereas the white seams
show a large increase in Ce contents. Therefore, REEs must
have been removed from the other parts of the profile, trans-
ported in solution and deposited as REE-bearing secondary
minerals.
In the weathered syenite, there is simultaneously an in situ
precipitation of REEs from the primary minerals and a con-
4432 J. J. Braun et al.
tribution to the growth of secondary phases of REEs and
some cations with similar geochemical behavior (Ba, Sr, Ca)
which were brought in the soil solutions. This is demonstmted
by the presence of phosphates with or without Ce-anomalies.
Barium and Strontium would be provided by the dissolution
of alkaline feldspars. An ICPAES analysis of a perthite sep-
arate gave 5000 and 1500 ppm of Ba and Sr, respectively.
When the water table falls, the soil solutions are more and
more confined and may be saturated in REE-Ba-Sr-Ca phos-
phates which ( 1) either precipitate in the dissolution cavities
of the weathered accessory minerals, or (2) grow at the ex-
pense of apatite crystals. The in situ replacement of apatite
by LREE phosphates has been proposed by JONASSON et al.
( 1985) and ELDERFIELDet al. ( 1981). SAWKA et al. ( 1986)
and MARIANO ( 1989) show that the secondary REE phos-
phates (florencite and rha~op~ne) are often depleted in
Ce. BANF~ELDand EGGLETON ( 1989) studied in detail the
weathering of apatite crystals from the Southern North Wales
Granite (Australia). In the weathered rock, the REE-bearing
assemblage is similar to that observed in this study. It consists
of donuts with complex chemical compositions including
florencite-( La), florencite-( Ce), and rha~ophane in which
Ba, Sr, and Ca are present. These phases are mixed with Fe-
Ti oxides. Aluminium is often in excess in the phosphate
donuts. Rhabdophane could precipitate in Al-free micro-
domains, On the other hand, DUDDY ( 1980), who studied
a weathering profile developed from a volcanogenic sandstone
(Southern Victo~a-Austria), invoked adsorption processes
to explain the enrichment in REEs, Ba, Sr, and Rb at the
weathering front. He concluded that REEs and the other ele-
ments would be adsorbed on the weathering products of bio-
tite, mainly swelling clays such as vermiculite in which up
to 10% of (La + Ce + Nd + Y) were present. However, no
particular attention was paid to study the presence of clay
sized REE-bearing minerals in the weathered sandstone.
The Upper Profile (Loose Nodular Horizon, Iron Crust,
and Mottled Clay Horizon)
In the upper horizons (loose nodular horizon, iron crust,
and mottled clay horizon) coupled mineralogical and geo-
chemical investigations of REEs are difficult because of the
strong weathering of this zone and the opacity caused by the
presence of iron oxides and clay minerals.
Iron crust and mottled clay horizon
In contrast to the mottled clay horizon, a distinction be-
tween white and red domains has not been made within the
iron crust. Calculations based on Th immobility show REEs
leaching in the iron crust to be similar to that observed in
the loose nodular horizon. The REEs are leached at the top
of the mottled clay horizon (zone c), whereas there is a jux-
taposition of accumulation and leaching zones at the bottom
(zones a and b). The white domains, characterized by both
illuviation and iron loss, are enriched in REEs while the red
domains, characterized by acidification generated by iron
precipitation (AMBROSI et al., 1986), are depleted in REEs.
REEs may be transported by clay scavenging.
Loose nodular horizon
The REEs which are retained in this horizon may be con-
tained either in resistant primary or secondary minerals or
adsorbed onto clays (PRICE et al., 199 1). In this acidic media
( pH c 6)) the probable REE-bearing secondary minerals are
generally phosphates ( STUMM and MORGAN, 198 1; MARI-
ANO, 1989). REE carbonates should only precipitate at higher
pH values, rarely encountered in the top horizons of lateritic
proliles ( HERBILL~N and NAHON, 1988). The relative ac-
cumulation of resistant zircon grains can provide a slight
enrichment in the heaviest REEs, especially in the sandy
fraction.
When ligands such as PO:-, CO’,- or organic acids are
absent from the solution, the affinity of surface minerals in-
creases from La to Lu ( ROALDSET, 1974: AAGAARQ 1974).
ELPRINCE et al. ( 1980) demonstrated that the selectivity of
La is stronger than Na and Ba on montmorillonite. SHOL-
KOVITZ( 1989) has shown the strong retention of 15’Eu, used
as a tracer in his experiments, on clayey sediments from Buz-
zard Bay, USA. When inorganic and organic ligands are
present, the LREEs are preferentially adsorbed on solid sur-
faces by comparison to HREE (BYRNE and KIM, 1990). In
the loose nodular horizon, REEs may be leached by acidic
rainwater and are perhaps more commonly transported in
suspended form than in soluble form. If an analogy is made
between the REE behavior in rivers and in soil solutions,
some assumptions may be reached on the REE state in the
Akongo profile. GOLDSTEINand JACOBSEN( 1988) suggested
that REEs are strongly controlled by pH, with highest levels
in acidic rivers. EL.DERFIELDet al. ( 1990) showed that 0.45
pm-filtered water samples from streams of North Yorkshire
have a strong negative correlation between Nd and pH. They
suggest that there are two major pools for the REE in rivers:
a colloidal reservoir of REE-rich particles having a shale-like
pattern and a dissolved reservoir characterized by HREE en-
richment. Recently, SHOLKOVITZ ( 1992) has clearly dem-
onstrated this fact, showing that both the solution and col-
loidal phases are HREE and LREE enriched, respectively,
reiative to the continen~l crust. Moreover, river colloids are
enriched in Ce, inducing negative Ce-anomalies in the filtered
river water. In the loose nodular horizon, soil solutions rich
in COZ and organic acids have a pH between 4 and 5. These
conditions would favor both the dispersion and the leaching
of clay particles within the profile. Considering the REE be-
havior in rivers, an assumption of LREE migration associated
with clays may be made in this part of the profile. Neverthe-
less, the loose nodular horizon of laterites which is the result
of poorly understood polyphased weathering processes, is a
place where the major and trace element behavior is difhcult
to define.
CONCLUSIONS
1) The REE and Th mass balance calculations for the host-
rock minerals show that at least 70% of the LREEs and
50% of the HREEs are found in allanite, apatite, titanite,
and epidote and at least 50% of the Th is controlled by
these same accessory minerals. These accessory phases
represent only about 2 wt% of the whole rock and are
destroyed during the early stages of weathering. Most of
 Geochemistry of REEs and Th in a lateritic soil profile
the REEs are released in the soil and are directly influenced
by weathering processes.
2) Comparison of the compositional change of Zr, Ti, and
Th as a fun~ion of the apparent density of the different
zones of the saprolite shows that Th is the least mobile
element and may be used as a tracer to calculate mass
balance.
3) The mobility of Zr and Ti is shown by the weathering
features on zircon grains and the presence of Ti with Ce
in the clayey seams. Thorium is precipitated in situ as an
oxide after the breakdown of the primary minerals. Sec-
ondary thorianite was identified.
4) The REEs are fractionated and redis~but~ in the sap-
rolite. The REEs are leached in the most weathered zones
and accumulated in the weathered syenite and in the white
clayey seams. The weathering products, which are com-
plex assemblages of aluminous REE phosphate and poorly
crystallized Ti-Fe-Al-Si phases, are strongly enriched in
LREEs. There is a transport of the REE in solution within
the saprolite which leads to ( 1) the deposition of cerianite
(CeOz) produced by the pH and Eh changes when the
water table moves and (2) the precipitation of the other
RED, especially LREEs, as aluminous phosphates de-
pleted in Ce at the bottom of the profile. Aluminous
phosphates without Ce-anomalies are also formed during
the incipient weathering of the REE-bearing accessory
minerals.
5) In the bottom of the mottled clay horizon, there is a jux-
taposition of leaching zones (red domains) characterized
by the dissotution of kaolinite andfor halloysite and ac-
cumulation zones (white domains) characterized by the
illuviation of the same clay minerals.
6) The majority of the REEs are leached from the Fe-rich
upper horizons (loose nodular horizon, iron crust, and
the top of the mottled clay horizon). Transport of the
REE associated with the clayey phase may be possible.
Acknowledgments-We are most grateful to the Yaoundt University
Soil Science staff and ORSTOM for facilitating the sampling at the
Akongo site. Annie Michard, Paul All&,Kupusami Govindaraju, Guy
Mevelle, Jean-Marie Claude, Alain Kohler, Jean-Michel Bertrand,
Jacques Yvon, and Frederic Viellieras are thanked for their technical
assistance with IDTiMS, SIMS, ICPMS, electron microprobe analyses,
scanning electron microscopy, and data processing. M. Wiedendeck
and L. Reisbek are thanked for their review of the manuscript and
the two GCA reviewers, P. Jakes and 1. R. Duddy, for their comments.
This project has been partly supported by a DBT-INSU grant ( AP
89/3828).
Editorial handling: T. Paces
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