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Ore Geology Reviews 33 (2008) 519 – 535

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Geochemistry of mineralization with exchangeable REY in the

weathering crusts of granitic rocks in South China
Zhiwei Bao ⁎, Zhenhua Zhao
Key Laboratory for Metallogenic Dynamics, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences,
Guangzhou, 510640, People's Republic of China
Received 8 June 2006; accepted 6 March 2007
Available online 19 April 2007

Abstract

Mineralization with exchangeable rare earth element (REE) and yttrium (MEX-REY) has been recognized in the weathering
profiles in South China since the early 1970's. This type of REY mineralization occurs in weathering profiles of parent rocks
ranging in composition from granite to acidic volcanic rocks and lamprophyre. The majority of the known resources occurring in
the weathering profiles of granitic rocks. Total resources of this type of REY amount to millions tons of rare earth oxides, and
therefore represent one of the most important types of rare earth resources in China, particularly for heavy rare earth elements
(HREE) and yttrium.
Accumulation of REY in the weathering profiles of granitic rocks is strongly controlled by the resistance to weathering of the
principal REY-bearing accessory minerals in the parent rocks; only a limited proportion of total REY (b 30%) is incorporated in the
rock-forming minerals. MEX-REY more commonly occur in weathering profiles developed on granitic rocks within which most of
the REY are incorporated in accessory minerals weakly resistant to weathering (doverite, parisite, etc.). For the well-developed
weathering profiles, three horizons can be distinguished from surface downwards: the lateritic horizon (A), the weathered horizon
(B), and the weathering front (C). Continuous leaching, coupled with low rate of denudation, results in the accumulation of REY in
the subsurface horizons (the B and C horizons), and thus results in REE differentiation within the well-developed, layered, and
mature weathering profiles. Exchangeable REY, which can be replaced by cations like NH4+ and Na+ etc. in electrolyte solutions
and can be removed by complexing agents such as EDTA, are commonly the major form of REE occurrence in the B horizon.
Cerium is enriched in the top layer (A horizon) and depleted in the subsurface horizons of the weathering profiles, most likely due
to the oxidation of Ce(III) to Ce(IV) followed by cerianite formation or absorption onto clays and/or Fe and Al oxyhydroxides.
© 2007 Published by Elsevier B.V.

Keywords: Weathering profiles; Ion-exchangeable rare earth element mineralization; Granitic rocks; South China

1. Introduction researchers have assumed that the REE compositions of

The rare earth elements (REE) have often been
considered to be relatively immobile. In fact, many
⁎ Corresponding author.
E-mail address: baozw@gig.ac.cn (Z. Bao).
0169-1368/$ - see front matter © 2007 Published by Elsevier B.V.
doi:10.1016/j.oregeorev.2007.03.005
river sediments reflect the REE compositions of the
weathered source materials, and used that to deduce the
provenance of sedimentary rocks. REE distributions
have also been used to obtain information about the
evolution of the earth, assuming that Sm and Nd are not
fractionated during chemical weathering (e.g., McLen-
nan, 1989; McLennan et al., 1993).
520 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
Numerous studies have, however, challenged the
above assumption and have shown that chemical
weathering causes REE mobilization and fractionation
(e.g., Martin et al., 1976; Goldstein and Jacobson, 1988;
Sholkovitz, 1992, 1995). Balashov et al. (1964) were
probably the first to have shown that the REE were
mobilized during intense chemical weathering under
warm and humid conditions. These authors suggested
that the heavy rare earth elements (HREE) were prefer-
entially transported in solutions. Leaching experiments
on silicate-dominated rocks, including granites, demon-
strated that REE were fractionated during alteration and
weathering. This was interpreted to be mainly controlled
by the dissolution and alteration of accessory minerals
(Möller and Giese, 1997; Möller, 2002). Although the
geochemical behavior of REE during weathering pro-
cesses cannot easily be generalized because of (1) the
wide variance of REE-bearing mineral assemblages (the
accessory minerals in particular) as well as their acces-
sibilities to fluids in both parent rocks and weathered
materials, and (2) the location-specific physicochemical
and biological factors of rock weathering (Fritz, 1988;
Price et al., 1991). REE mobility and differentiation have
subsequently been observed in weathering profiles
ranging from warm, humid to cold, semiarid conditions
(Floss and Crozaz, 1991; Boulangé and Colin, 1994;
Braun et al., 1998; Patino et al., 1998; Sharma and
Rajamani, 2000). REE mobility and accumulation in
weathering profiles at concentrations much greater than
that observed in the fresh bedrocks have been reported
(Nesbitt, 1979; Duddy, 1980; Topp et al., 1984;
Middelburg et al., 1988; Nesbitt and Markovics, 1997).
Fig. 1. Distribution of mineralization with exchangeable REY and the studied deposits. The shaded box shows the major area of deposits containing
exchangeable REY. 1. Heling REE deposit; 2. Longnan REE deposit; 3. Guposhan REE deposit; 4. Huashan REE deposit.
Furthermore, ion adsorption was suggested to be the
major cause of secondary enrichment of the REEs in the
weathering process (Roaldset, 1973; Öhlander et al.,
1996).
From the early 1970's onwards, ores with exchange-
able REE and yttrium (henceforth referred to as MEX-
REY and often referred to as “easily worked deposits of
REE” in the English literature; Neary and Highley, 1984)
have become an important REE mineral resource in
China. The total reserves of this type of REY deposit have
reached millions of tonnes of rare earth oxides and they
form particularly significant resources for HREE and Y.
No REE mineralization of this type has, to our knowledge,
been reported outside China. In China, the MEX-REY
deposits mainly occur in the areas south of 28°N, namely
in the provinces of Jiangxi, Hunan, Guangdong, Guangxi,
and Fujian, where the climate is sub-tropical (warm and
humid with annual precipitation of over 1500 mm). About
90% of the known ion-exchangeable REY resources in
China are located in Jiangxi, Guangdong and Guangxi
(Fig. 1). Since the topography of the region is dominated
by low hills, denudation rates are relatively low and the
weathering profiles are well preserved. Generally, the
weathering profiles in these regions commonly range
from 15 to 35 m, but can be as much as 60 m locally.
Known areas of REY mineralization outcrop total about
90,000 km2, and a total of 214 MEX-REY deposits
have been explored to date. The annual output of rare
earth oxides from this type of REY mineralization has
reached 10,000 tons. The weathering profiles are clearly
zoned, while the compositions and textures change
gradually. REY enrichment in the subsurface horizons
 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535 521

of the weathering profiles is similar in amongst all
deposits; those containing more than 500 ppm ion-
exchangeable REY with commercially significant sizes
are considered as ores. Most of the known ion-
exchangeable REY deposits of China are hosted in the
weathering profiles developed from granitic parent rocks,
and a few from pyroclastic rocks, tuffs, and lamprophyres.
This study investigated four ion-exchangeable REY
deposits in South China. The aims were to investigate
factors, including the mineralogical assemblages of the
parent rocks, which control the REY accumulation and
differentiation in the weathering profiles.
2. Main geological characteristics of the parent rocks
Known ion-exchangeable REY deposits of China
occur mainly in the weathering profiles of granitic parent
rocks, particularly highly evolved Mesozoic granitic
rocks that are REY-rich. REE mobilization and accumu-
lation in the weathering profiles appears to be controlled
by the parent rock mineralogy, specifically the distribu-
tion of REY in the primary REY-bearing minerals, the
stability of these minerals during weathering, and their
abundance in the parent rock (e.g., Humphris, 1984).
The four ion-exchangeable REY mineralized granitic
rocks were selected in this study according to their
economic significance and variation of details. The
Xinxiu granite and Heling granite-porphyry, Jiangxi
Province, represent HREE+ Y and light REE (LREE)
ion-exchangeable REY mineralization, respectively. The
Huashan and Guposhan granites, Guangxi and Hunan
Provinces, represent parent rocks with REY mainly oc-
curring in accessory minerals that are moderate to strongly
resistant to weathering. The latter led to two types of REY

Fig. 2. Geological maps of (A) the Xinxiu granite (after Huang et al., 1989); and (B) Heling porphyry (after Zhang and Ye, 1995).
522 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
mineralization in the weathering profiles: accumulations
(as well as placers) of REY-rich accessory minerals and;
ion-exchangeable mineralization.
2.1. Xinxiu granite
The Longnan REY deposit occurs in the weathering
profile of the Xinxiu Granite, Longnan County, Jiangxi
Province. The mineralized area is about 40 km2 at sur-
face; the average thickness of the orebody is around
10 m, but can be up to 29 m locally. The orebody is thick
at the top and thin at the base of the hills. The Xinxiu
Granite intruded into a sequence of tuffs, rhyolite and
rhyodacite of the Late Jurassic Shetianqiao Group
(Fig. 2A). The Xinxiu Granite is mainly a medium- to
coarse-grained biotite granite, medium-grained musco-
vite granite, and biotite–muscovite granite. The em-
placement age of the granite was dated at 147.7 ± 3.0 Ma
using the Rb–Sr isochron method (Huang et al., 1989).
Its initial 87Sr/86Sr value of 0.7188 ± 20, and its compo-
sition is within the range of S-type granite. From west to
east, the petrography of the granite changes gradually
from medium- to fine-grained muscovite granite to
medium- to coarse-grained biotite granite. Correspond-
ingly, the chondrite-normalized REE patterns of the
rocks change from left-dipping (LREE/HREE ∼ 0.74) to
right-dipping (LREE/HREE ∼ 2.4) (Huang et al., 1989).
REY distribution in the muscovite granite shows that
rock-forming minerals (plagioclase, K-feldspar, quartz
and muscovite) account for ca. 28% of REY in the whole
rock, thus implying that ca. 72% REY occur in the
accessory minerals (Table 1). The accessory mineral
assemblage of the muscovite granite and the biotite
granite are significantly different, which may account for
the difference in the degree of REY enrichment in the
weathering profiles. The accessory minerals in musco-
vite granite consist mainly of doverite, fluorite, zircon,
and minor monazite, gadolinite-(Y), xenotime-(Y), and
chernovite-(Y). Doverite, a HREE-rich accessory min-
Table 1
∑REE + Y portions in the Xinxiu muscovite granite, Huashan and Guposhan biotite granites
Parent rock Rock-forming minerals
Xinxiu muscovite granite Plagioclase (11%), quartz (9%),
K-feldspar (6%), muscovite (2%),
28%
Huashan biotite granite Biotite (11%), plagioclase (6%),
K-feldspar (5%), quartz (2%)
24%
Guposhan biotite granite Plagioclase (14%), biotite (11%),
K-feldspar (1%), quartz (1%)
27%
The minerals (both rock-forming and accessory minerals) are arranged in the order of descending importance for hosting REE + Y in the whole rocks.
eral in the muscovite granite, hosts about 60% REY of
the whole rock, and contributes greatly to REY accumu-
lation in the weathering profile owing to its weak resis-
tance to weathering. In contrast, the accessory mineral
assemblage of the biotite granite is rather simple
(monazite, xenotime-(Y), zircon, minor apatite and
fluorite) and less vulnerable to chemical weathering.
Both biotite granite and muscovite granite had under-
gone a series of episodes of hydrothermal alteration,
including albitization, muscovitization, fluoritization
and carbonatization; the muscovite granite was more
extensively altered than biotite granite, which is pos-
sibly the cause of the difference in accessory mineral
assemblages.
2.2. Heling porphyry
The Heling REY deposit is located in Xunwu County,
Jiangxi Province. The REY mineralization mainly
occurs in the weathering profile of a granite-porphyry
body. The thickness of the orebody is about 8 to 9 m
on average, and can be up to 28 m locally. The granite-
porphyry (with an outcrop area of about 32 km2)
intruded in a Mesozoic volcanic sequence in the Heling
volcanic basin. Whole rock Rb–Sr isochron dating of the
volcanic sequence varies from 138 to 154 Ma (Lai and
Wang, 1996). The Heling granite-porphyry is considered
to be part of the Jilongzhang Formation of the Upper
Jurassic Changpu Group acidic volcanic rocks (Lai and
Wang, 1996; Zuo et al., 1999, Fig. 2B). The granite-
porphyry is 4.1 km wide and 8.6 km long. Phenocrysts
are plagioclase feldspar (∼40%), K-feldspar (15–40%),
quartz (15–30%), and biotite (∼ 2%), and the matrix is
mainly of quartz and feldspar. REY-hosting accessory
minerals include bastnaesite-(Ce), apatite, zircon, and
minor monazite, tourmaline, fergusonite, doverite,
fluorite, etc.; the two LREE-rich accessory minerals,
bastnaesite-(Ce) and apatite host the majority of the
REY.
Accessory minerals
Doverite (65%), fluorite (3%), xenotime-(Y) (1%),
monazite (1%), zircon (1%),apatite
72%
Monazite, allanite, and zircon, apatite,
fergusonite-(Y), xenotime
76%
Fergusonite-(Y), allanite, xenotime,
monazite, apatite, zircon, gadolinite
73%
 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
2.3. Huashan and Guposhan granites
The Huashan and Guposhan Granites (with outcrop
areas of N500 km2 each) are located in the western part of
the EW-striking Nanling Orogen, in the border areas of
Guangxi and Hunan Provinces. They intruded into
Paleozoic sedimentary rocks, which comprise of Devo-
nian sandstone, shale and limestone and the Ordovician
and Silurian slate, phyllite and shale, with slight meta-
morphism and skarn-hydrothermal tin mineralization in
the contact zone. The two plutons show porphyritic
structures, except the marginal phase of the Guposhan
granite. Microcline-perthite occurs as the main pheno-
crysts, in amounts ranging from 10 to 35%v/v. Matrix
minerals include microcline-perthite, plagioclase,
quartz, and biotite. Hornblende occurs in the marginal
phase of the Huashan granite and the central phases of
the Guposhan granite as a minor rock-forming mineral.
The disseminated magmatic REE mineralization in both
granites was discovered in the early 1960's. The weath-
ering profiles of the granite as well as the placers were
mined for fergusonite-(Y) and cassiterite for many years
(Institute of Geology, Chinese Academy of Sciences,
1965).
The Huashan granite consists of three intrusive stages:
(1) the Niumaio quartz monzonitic granite (163 ± 4 Ma,
Zircon SHRIMP; Zhu et al., 2006) and Tong'an quartz
monzonite (160 ± 4 Ma, Zircon SHRIMP; Zhu et al.,
2006); (2) the Huashan main-body, medium- to coarse-
grained (porphyritic amphibole) biotite granite (162 ±
1 Ma, Zircon SHRIMP; Zhu et al., 2006); and (3) the
Meihua and Yinping fine-grained granites (148 ± 4 Ma,
Zircon LA-ICPMS; Zhu et al., 2006). The Huashan main-
body, a coarse- to medium-grained biotite granite, can be
further divided into three intrusive phases: the marginal
phase including a contaminated zone, the main phase and
the top marginal phase. The main-body biotite granite has
high SiO2 (∼75.42%) and alkaline contents (Na2O
∼2.61%, K2O ∼5.30%). Initial 87Sr/86Sr ratios of the
early stage and main-body are 0.70472–0.70572 and
0.70633–0.70714, respectively (Zhu et al., 2006). εNd(T)
and δ18O values of the early stage and main-body are in
the range −0.37 to −3.2, and 8.4‰ to 10.9‰, respec-
tively (Zhu et al., 1989, 2006). It is thus suggested that the
Huashan granite (except the late stage fine-grained
granite) is an I-type granite (Zhu et al., 1989, 2006).
The MEX-REY potential has been explored in the well-
developed weathering profiles on the main-body of the
Huashan granite.
The Guposhan coarse- to medium-grained amphibole
biotite granite can also be divided into three phases: the
central phase, intermediate phase (163 ± 4 Ma, zircon LA-
523
ICPMS; Zhu et al., 2006) and marginal phase (162 ± 3 Ma,
zircon SHRIMP; Zhu et al., 2006). The intermediate phase
is a biotite granite, similar to the biotite granite from the
Huashan granite main-body, has high SiO2 (∼74.71%)
and is alkaline rich (Na2O ∼3.57%, K2O ∼4.97%). The
initial 87Sr/86Sr ratios of Guposhan granites vary in the
range of 0.70644–0.70742, while the εNd(T) values vary
in a narrow range of −1.7 – −3.1 (Zhu et al., 2006). The
new data show that Huashan–Guposhan granites are I-
type granites, even though some previous studies sug-
gested that the Guposhan granite is S-type (Geological
Department of Nanjing University, 1981; Gong et al.,
1985; Zhang et al., 1985; Yang and Zhang, 1991).
Study of the biotite granite of the Guposhan main
phase and the main-body of the Huashan granite shows
that rock-forming minerals, including plagioclase, biotite,
K-feldspar, and quartz host about 27% and 24% REY of
the whole rock REY, respectively. Observations show that
biotite often contains fine-grained inclusions of accessory
minerals such as zircon and monazite, which means that
the REE + Y contents of biotite is likely lower than those
listed in Table 1 (e.g., ΣREE + Y = 520.8 ppm in biotite
granite from the Guposhan granite). The accessory
mineral assemblage in the Huashan Granite main body
includes magnetite, ilmenite, monazite and zircon. Minor
accessories include allanite, titanite, apatite; fergusonite-
(Y), thorite and xenotime occur only in the intermediate
and top marginal phase. The Guposhan Granite contains
more zircon and fergusonite than the Huashan Granite,
especially in the marginal phase together with fluorite,
and increased amount of gadolinite. Monazite, ferguso-
nite-(Y), and allanite are the three major REE + Y-hosting
accessory minerals in the two granites, accounting for the
largest portion of REE + Y.
2.4. Accessory mineral controls on REE enrichment in
the weathering profiles
The importance of accessory minerals as hosts for REE
in granitic rocks is supported by many other studies, which
show that most of the REE is incorporated in accessory
minerals; only a small portion of the REE exists in rock-
forming minerals (Alderton et al., 1980; Grommet and
Silver, 1983; Sawka and Chappell, 1988). The rock-
forming minerals account for 24% to 28% of REY of the
whole granitic rocks in the three studied granites; acces-
sory minerals accounting for most of the REY (Table 1).
The main REY-hosting accessory minerals include
bastnaesite, parisite-(Y), gadolinite-(Y), doverite, allanite,
xenotime, monazite, etc. The proportions, and thus impor-
tance of the principal REY-bearing accessory minerals
may, however, vary in the different granites.
524 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
The behaviors of the major REY-bearing accessory
minerals during chemical weathering are decisive factors
affecting the accumulation of ion-exchangeable REY
and differentiation of REE in the weathering profiles.
Accordingly, the REY-bearing accessory minerals can be
subdivided into three groups: (1) strongly resistant to
weathering, such as xenotime and zircon; (2) moderately
resistant to weathering, these including fergusonite,
monazite, allanite, etc.; and (3) weakly resistant to
weathering, such as bastnaesite, parisite, gadolinite-(Y),
doverite, and so on (Wu et al., 1993). For granitic rocks
in which the REY are mainly hosted in accessory
minerals that are weakly resistant to weathering
(bastnaesite, parisite, gadolinite-(Y), doverite etc.), as
in the cases of the Xinxiu granite and Heling granite-
porphyry, MEX-REY was developed in the weathering
profiles only. For example, in the Xinxiu muscovite
granite, doverite relicts can only be observed in Horizon
C and rarely in Horizon B, the breakdown of doverite
that hosts most of the HREEs and Y led to the prefer-
ential enrichment of HREEs and Y in the weathering
profile. On the other hand, LREEs are preferentially
enriched within the weathering profile of Heling Granite
due to the fact that most of the REY in the parent rock
occurs in LREE-enriched accessory minerals, such as
bastnaesite and Ce-apatite (weakly resistant to weather-
ing). Relicts of bastnaesite can only be observed in
Horizon C and Ce-apatite relicts are rarely seen in the
upper part of Horizon B. Both ion-exchangeable and
placer REY deposits may be developed for the rocks
within which the REY are primarily incorporated in
accessory minerals that are moderately and highly resis-
tant to weathering. The Guposhan and Huashan granites
are examples where the REY are mainly concentrated in
monazite, fergusonite and xenotime. These minerals can
be observed in the whole weathering profile even though
they often have yellowish to brown coating films, which
resulted in the development of ion-exchangeable REY
mineralization in the weathering crust and also placer
REY deposits in the alluvial cover.
3. REE distribution patterns
3.1. REE accumulation and differentiation in the weath-
ering profiles
To study the weathering profiles developed from
granitic rocks, the profiles were divided into three hori-
zons from surface downwards: (A) the lateritic horizon,
(B) the weathered horizon, and (C) the weathering front.
The reddish colored lateritic horizon (A) is commonly 1
to 2 m thick and can be up to 10 m thick in local areas of
extensive leaching and very low rate of denudation. It
consists mainly of quartz and clay minerals (∼ 50%).
The weathered horizon (B), commonly reddish to yel-
lowish or light gray in color, is composed of frail and
loose materials and can be further subdivided into
extensively-weathered (B1) and weathered horizons
(B2). The B1 extensively-weathered horizon consists
of b 15% K-feldspar and around 40% clay minerals (2 to
5 m thick in the study areas); the B2 weathered horizon
consists 15 to 25% K-feldspar and about 30% clay
minerals (10 to 20 m thick in the study areas). The
weathering front, C horizon, is mostly light gray in
color, has textures of parent rocks and contains b 20%
clay minerals (3 to 5 m thick in the study areas).
The clay mineral assemblages change from hydro-
mica and montmorillonite to halloysite (7 Å) and
kaolinite to gibbsite (plus hematite) in the weathering
profiles. The content of halloysite (7 Å) decreases from
the C to B horizons and diminishes in the A horizon, and
correspondingly, the crystallinity of kaolinite also tends
to decrease (Yang, 1987; Wu et al., 1989; Bao, 1992;
Qiu and Bao, 1992), interpreted as results of continuous
acidic percolation. Scanning electron microscopy indi-
cated that the morphology of kaolinite in the weathering
profiles is irregular plates with diameters ranging from 1
to 2 μm; the halloysites are pipe-like in shape, with
lengths of 0.5 to 2 μm (Yang, 1987). Accordingly, as the
degree of weathering increases, the contents of Ca, Mg,
Na, and K decrease, and the weathered materials
become more and more Al enriched (Table 2; Fig. 3).
The Chemical Index of Alteration (CIA) values (Nesbitt
and Young, 1982, 1984), calculated from the chemical
analysis of the weathered materials and parent rocks
using the molecular proportions of Al2O3, Na2O, K2O,
and CaO (CIA = [Al 2 O 3 / (Al 2 O 3 + Na 2 O + K 2 O +
CaO⁎)] × 100, where CaO⁎ is in silicates), increase as
the weathering process proceeds. For example, CIA
values increase from 50 in the parent rock to 90 in the
lower part of horizon A within a profile from the Xinxiu
granite, and change from 53 in parent rock to 98 in the
horizon A within the weathering profile of the Heling
granite-porphyry. SiO2, K2O, and Na2O contents of the
clay-sized fraction increase gradually from the surface
downwards of the weathering profiles, whereas reverse
trends were observed for the Al2O3 and Fe2O3 contents
(Song and Shen, 1986). The abrasion pH values of the
weathering materials (b20 mesh) were determined using
0.01 M CaCl2 solution at solid/liquid ratios of 1:1
extraction, after stirring for 5 min and measuring after
20 min. Results show that the abrasion pH values in the
weathering profile vary from 4.2 in the A horizon to 5.5
to 6.0 in the B horizon and 6.5 in the C horizon. The
 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535 525

Table 2
Major chemical compositions (%wt) of weathered materials and parent rocks from the Xinxiu and Heling profiles and the Huashan and Gposhan
biotite granites
Xinxiu profile a Heling profile
Oxides A A B1 B2 C C Moscovite granite A B1 B1 B2 Granite-porphyry
SiO2 66.49 68.42 75.16 74.94 72.46 76.90 76.14 48.06 48.54 49.22 51.38 70.14
TiO2 0.07 0.05 0.03 0.06 0.03 0.14 0.03 0.54 0.50 0.52 0.50 0.50
Al2O3 21.17 20.09 15.82 15.25 15.98 12.39 12.97 34.69 32.56 32.47 30.18 14.79
Fe2O3 1.23 1.22 0.93 0.73 0.55 0.44 0.09 1.75 1.63 0.98 1.55 2.09
FeO 0.23 0.16 0.09 0.68 1.00 0.78 1.07 0.01 0.11 0.11 0.07 0.50
MnO 0.15 0.16 0.11 0.00 0.03 0.08 0.03 0.05 0.03 0.05 0.10 0.05
MgO 0.03 0.03 0.06 0.08 0.12 0.06 0.07 0.15 0.11 0.33 0.35 0.75
CaO 0.11 0.07 0.07 0.11 0.11 0.40 0.62 0.09 0.09 0.18 0.21 0.33
Na2O 0.00 0.10 0.01 0.27 0.71 3.76 4.25 0.01 0.01 0.08 0.59 3.23
K2O 1.91 1.32 2.01 3.48 5.35 4.43 4.52 0.62 0.68 2.20 4.90 6.83
P2O5 0.02 0.02 0.01 0.02 0.02 0.02 0.02 0.02 0.02 0.05 0.05 0.05
LOI 8.28 8.14 5.90 4.92 3.78 1.12 0.96 11.75 11.77 10.56 7.87 1.06
Total 99.69 99.78 100.20 100.54 100.14 100.52 100.77 99.74 96.05 96.76 97.75 100.32
CIA 90 92 87 77 69 51 50 98 97 92 82 53
Note: CIA = Chemical Index of Alteration.
a
Data from Wu et al., 1989.

cation exchange capacities of the whole weathering ions such as NH4+, H+, Na+, K+, etc. under neutral and/
profile (except the lateritic zone, the A horizon) are or acidic conditions, and can also be removed by com-
similar (Yang, 1987), and no obvious selective adsorp- plexing agents such as ethylenediaminetetraacetic acid
tion of REY was observed for the clay minerals ex- (EDTA) and ethylene glycol tetraacetic acid (EGTA).
tracted from the weathering crusts in pH range of 3 to 6 Some studies show that the REE adsorbed onto clay
(Song and Shen, 1982). Thus, the weathering profile can minerals in weathering profiles developed on granitic
be roughly considered as a non-selective ion exchange rocks is mainly in simple ionic state (Song and Shen,
column. 1982, 1986). The simple ionic state of REE in weath-
This study has shown that REY in the weathering ering profiles is also supported (even though somewhat
profiles of granitic rocks exists in two major forms, indirectly) by the studies of REE in natural waters (Baes
REY-bearing accessory minerals and ion-exchangeable and Mesmer, 1976; Goldstein and Jacobson, 1988),
REY in the clay minerals. This is controlled by the
behavior of the main REY-bearing accessory minerals
in the parent rocks during weathering (Table 3). For
granitic rocks within which the main REY-bearing ac-
cessory minerals are those that easily breakdown during
chemical weathering, ion-exchangeable REY will be the
major form in the B horizon. The Xinxiu muscovite
granite and Heling granite-porphyry are two examples;
proportions of ion-exchangeable REY in the B horizons
are as high as 85% and 92%, respectively. In contrast,
with exactly the same weathering conditions, only 46%
REY are in ion-exchangeable form in the B horizon
of weathering profile developed on the Xinxiu biotite
granite (Table 3). The different proportions of ion-
exchangeable REY in weathered materials of the mus-
covite granite and the biotite granite is probably a result
of the differences in major REY-bearing accessory
minerals and their resistance to chemical weathering. It Fig. 3. Trend of Al2O3, K2O, CaO and Na2O variation (wt.%) in the
is possible that ion-exchangeable REY in the weathered weathering profiles developed on the Huashan and Xinxiu granite and
materials can be replaced by electrolyte solutions with Heling granite-porphyry in South China.
526 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535

which suggest that in the weak acidic pH range, free ion

REE3+ are the predominant aqueous species in natural
waters (Fig. 4).
Our analyses on the four weathering profiles de-
veloped on the Xinxiu, Huashan, and Guposhan gran-
ites, and the Heling granite-porphyry show that REY are
enriched in the B horizon with strongly REE differen-
tiation (Table 4). The REY are concentrated mainly in
the B horizon and less strongly in the C horizon. The
REY contents of the B horizon can be enriched to 2 to 4
times higher than in the parent rocks. In the weathering
profile of the Xinxiu muscovite granite the REY are
enriched in the B horizon to the degree up to three times
higher than those in the parent rock (Fig. 5). As shown
in Fig. 5, the REY contents are relatively low in the A
horizon and C horizon, suggesting depletion of REY
during weathering process, probably due to the exten-
sive leaching and low cation exchange capacity of the
clay minerals. The ion-exchangeable REY removed this
way were likely re-adsorbed onto the clay minerals at
the deeper part of the weathering profile. Similar trends
of REY enrichment and differentiation are observed
in weathering profiles developed on the Huashan,
Guposhan, and Heling granitoids.
The chondrite-normalized REE patterns, as well as
the parent rock-normalized REE patterns of samples
from profiles developed on the Xinxiu muscovite gran-
ite, Huashan and Guposhan biotite granite and Heling
granite-porphyry, consistently show REE enrichment in
the B horizon and depletion in A horizon (Fig. 6A–F).
In the B horizon of Heling profile, the REY contents are
enriched to more than 4 times that of the parent granite-
porphyry. In the lower part of the weathering profile (C
horizon) near the bedrock, i.e., at the initial stage of
granite weathering, the REE (especially LREE) plus Y
are depleted. This was likely due to preferential removal
of LREE during weathering as shown in the Xinxiu
profile (Fig. 5). As shown by REE patterns, the REE
accumulation in the profile are largely controlled by the
Fig. 4. Model calculation of total (free ion + complexed) REE
concentrations in solutions normalized to free ion REE3+ concentra-
tions for typical rivers of pH = 6 and pH = 8 (Goldstein and Jacobson,
1988).
major REE bearing accessory minerals; for example,
HREE accumulation in the weathering profile devel-
oped on the Xinxiu muscovite granite is largely due to
doverite being weakly resistant to weathering which
hosts large portion of REY especially HREE and Y
(Fig. 6A,B). In comparison with the parent rocks, the A
and B1 horizons are relatively enriched in LREE, while
the B2 horizon and upper part of the C horizon are
relatively enriched in HREE (Fig. 7). Ce is enriched in
the A horizon and upper part of the B horizon. Positive
Ce anomalies, calculated by the formula:
CeN
Ce=Ce⁎ ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
LaN  PrN
where CeN, LaN, and PrN represent the chondrite-
normalized values of Ce, La, and Pr, respectively, are
observed in the upper parts of the studied profiles. Nega-
tive Ce anomalies are observed in the B and C horizons
(Fig. 8).
Since ion-exchangeable REY make up the largest
fraction of the REY in the weathered materials (except in
horizon A), REE contents of clay minerals (b2 μm) in

Table 3
REE portion in the weathered materials of horizon B from Xinxiu and Heling weathering profiles
Profile REE occurrence Portion (%)
Xinxiu (Zudong) weathering crust Ion-exchangeable REE adsorbed on clay minerals 85
developed on muscovite granite Rock-forming minerals (K-feldspar, quartz, muscovite) 8
Accessory minerals (including xenotime, monazite, gadolinite-(Y), and zircon) 7
Xinxiu (Zudong) weathering crust Ion-exchangeable REE adsorbed on clay minerals 46
developed on biotite granite Rock-forming minerals (K-feldspar, quartz, and biotite) 9
Accessory minerals (including xenotime, monazite, zircon) 45
Heling weathering crust developed Ion-exchangeable REE adsorbed on clay minerals 92
on granite-porphyry Rock-forming minerals (K-feldspar, quartz, and biotite) 2
Accessory minerals (including chenovite-(Y), fergusonite, monazite, 6
bastnaesite-(Ce), doverite, fluorite, and zircon)
Table 4
REY distributions in weathering profiles developed on granitic rocks from South China (ppm)
Profile Sample Horizon Depth La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y ∑REE + ∑REE LREE/ Eu/ Ce/
No. (m) Y HREE Eu⁎ Ce⁎
Xinxiu LN-1 A 0.5 21.36 47.18 5.17 17.58 4.14 0.50 4.35 0.75 4.94 0.99 3.05 0.49 3.55 0.52 27.95 142.52 114.57 5.15 0.36 1.10
profile LN-2 B1 2 25.71 38.18 9.13 46.52 25.09 0.42 28.46 4.27 24.62 4.92 15.00 2.51 17.86 2.79 121.60 367.08 245.48 1.44 0.05 0.60
LN-3 B1 3.5 34.39 26.99 11.11 57.32 45.05 0.40 90.12 17.82 117.54 23.72 70.12 11.48 75.46 11.36 635.00 1227.90 592.88 0.42 0.02 0.33
LN-4 B1 5 16.52 19.77 6.14 30.83 22.70 0.26 54.97 12.63 87.75 17.60 53.21 8.31 58.06 8.52 551.40 948.67 397.27 0.32 0.02 0.47
LN-5 B2 6.5 15.69 29.62 5.92 30.22 20.91 0.18 45.28 10.17 74.01 15.30 45.12 7.02 47.32 7.19 498.00 851.92 353.95 0.41 0.02 0.74
LN-8 B2 8 8.11 17.81 3.63 16.84 12.04 0.09 24.86 5.47 40.02 8.27 25.76 4.12 29.09 4.41 268.40 468.90 200.52 0.41 0.02 0.79
LN-9 C 9.5 8.86 14.34 2.65 13.90 8.50 0.10 15.05 3.27 23.98 4.90 15.04 2.60 16.18 2.55 145.20 277.12 131.92 0.58 0.03 0.71

Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535

LN-18R Muscovite 15.58 24.66 5.28 22.97 11.66 0.15 15.81 3.18 22.02 4.70 13.72 2.36 14.48 2.15 183.30 342.02 158.72 1.02 0.03 0.65
granite
Guposhan HK-1 A 0.5 84.40 361.40 24.55 93.43 15.68 0.98 16.42 1.94 12.05 1.83 7.15 0.77 6.45 0.82 71.43 699.30 627.87 12.20 0.19 1.90
profile HK-2 B1 1.5 184.60 341.80 51.25 206.30 31.86 0.61 27.69 3.19 22.77 2.86 13.59 0.69 11.89 0.92 138.20 1038.22 900.02 9.77 0.06 0.84
HK-3 B1 2.5 343.70 145.40 83.11 306.20 51.50 3.55 36.98 3.78 22.29 3.79 12.10 1.37 10.28 1.23 128.80 1154.08 1025.28 10.10 0.25 0.21
HK-4 B1 3.5 311.90 123.10 66.20 242.80 51.60 3.29 47.18 5.46 29.21 4.88 15.32 1.94 13.52 1.74 165.50 1083.64 918.14 6.70 0.20 0.21
HK-5 B1 4.5 375.00 199.10 72.67 257.40 61.70 4.24 68.32 7.11 36.76 6.75 19.62 2.52 17.67 2.52 192.80 1324.18 1131.38 6.02 0.20 0.29
HK-6 B2 5.5 290.80 163.30 55.44 194.00 47.82 2.85 54.78 4.30 21.79 3.54 11.32 1.44 10.87 1.49 98.79 962.53 863.74 6.89 0.17 0.31
HK-7 B2 6.5 218.40 153.80 42.35 151.10 34.59 2.50 62.14 10.34 55.32 10.23 27.95 3.61 22.16 3.11 273.00 1070.60 797.60 3.09 0.16 0.38
G-3R Biotite 53.95 102.80 12.72 39.04 8.15 0.54 6.48 1.14 6.83 1.40 4.06 0.68 4.50 0.66 37.41 280.36 242.95 8.43 0.23 0.94
granite
Huashan Hua95-1 A 0.5 63.27 247.00 12.95 45.11 7.40 0.92 9.35 0.82 5.23 0.51 2.83 0.08 2.41 0.11 31.49 429.48 397.99 40.80 0.34 2.10
profile Hua95-3 B1 2.5 104.70 274.80 22.95 77.50 13.31 1.50 14.11 1.45 8.42 1.16 3.74 0.23 3.53 0.36 47.71 575.47 527.76 29.50 0.33 1.30
Hua95-5 B1 4.5 130.60 226.10 25.66 81.46 14.51 1.87 11.15 1.83 9.62 1.73 4.67 0.67 4.48 0.63 44.95 559.93 514.98 24.50 0.45 0.94
Hua95-7 B1 6.5 92.07 161.30 22.28 80.67 14.29 2.43 13.54 1.38 9.76 1.45 5.11 0.57 5.34 0.75 64.54 475.48 410.94 22.80 0.53 0.85
Hua95-9 B2 8.5 124.10 206.70 29.29 107.80 20.47 4.30 22.26 2.83 18.08 3.37 10.07 1.34 10.03 1.34 117.40 679.38 561.98 13.50 0.62 0.82
Hua95-11 B2 10.5 133.00 182.50 24.99 86.22 13.81 2.14 16.54 1.68 15.42 2.44 8.41 0.94 7.79 0.76 114.70 611.34 496.64 15.50 0.43 0.76
Hua95-13 C 12.5 113.20 150.00 24.96 86.84 16.44 2.89 18.26 2.52 17.56 3.22 9.51 1.26 9.23 1.19 121.40 578.48 457.08 11.20 0.51 0.67
Hua-2R Biotite 71.41 124.40 15.15 45.80 9.07 1.22 6.99 1.23 6.56 1.29 3.61 0.59 3.74 0.56 34.10 325.72 291.62 14.00 0.47 0.91
granite
Heling HL-3-1 B1 1.5 364.80 709.60 88.23 306.60 35.96 3.58 15.28 2.20 8.26 1.77 4.38 0.75 4.17 0.64 37.55 1583.77 1546.22 40.30 0.47 0.95
profile HL-3-2 B1 3.5 934.00 167.90 186.70 729.80 83.23 8.51 28.32 3.33 13.44 3.13 6.35 0.83 5.55 0.81 56.38 2228.28 2171.90 34.20 0.54 0.10
HL-3-3 B1 5.5 504.50 89.30 90.96 341.10 54.84 7.53 34.28 4.36 19.35 3.61 8.80 1.23 7.41 1.06 82.89 1251.22 1168.33 13.60 0.53 0.10
HL-3-4 B1 7 1239.00 171.60 243.20 933.90 110.70 12.22 42.21 4.95 18.96 4.02 8.82 1.42 7.59 1.02 79.64 2879.25 2799.61 30.50 0.55 0.07
HL-3-5 B2 8.5 1600.00 273.80 301.20 1150.30 158.20 18.33 72.56 8.49 33.76 6.88 15.15 2.20 12.86 1.83 141.20 3796.76 3655.56 22.80 0.52 0.09
HL-3-6 B2 10 1064.00 119.90 191.80 717.70 107.80 13.84 57.01 6.77 18.62 5.52 12.68 1.90 10.64 1.54 119.40 2449.12 2329.72 19.30 0.54 0.06
HL-3-7 B2 11.5 460.40 129.50 80.34 308.60 52.96 7.28 35.72 4.97 21.20 3.97 9.85 1.49 7.90 1.19 87.42 1212.79 1125.37 12.00 0.51 0.16
HL-4R Granite- 189.70 338.80 40.09 131.10 21.66 2.20 15.08 2.25 9.67 1.84 4.61 0.77 3.88 0.61 45.43 807.69 762.26 18.70 0.37 0.93
porphyry
Note: Samples from the Xinxiu and Heling profiles were analyzed using ICP-AES, and the others were analyzed using XRF.

527
528 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535

Fig. 5. REE enrichment and differentiation within the weathering profile developed on the Xinxiu muscovite granite, Longnan County. (LREE/
HREE)s/p represents the ratio of LREE/HREE ratio of the weathered material vs. that of the parent rock; (REE + Y)s/p = content of REE plus Y of
weathered material vs. that of the parent rock. Ce anomalies (Ce/Ce⁎) range from 3.7 to 5.5 in upper part (0–0.7 m deep) of the weathering crust were
reported by Wu et al. (1989). A: lateritic horizon; B: weathered horizon; C: weathering front.

weathering profiles of Xinxiu and Heling Granites were
extracted and analyzed using INAA methods (Yang,
1987; Bao, 1992). Results show that more than 90%
REE in clay minerals are ion-exchangeable and the REE
contents of clay minerals are usually 1.5 to 2 times that
of the bulk weathered materials. REE concentrations
(La, Ce, Nd, Sm, Eu, Tb, Yb, Lu) of 8800 ppm in the
clays from the Heling profile were recorded. Clay
minerals from lower parts of the weathering profile are
relatively enriched in HREE. Comparing with North
America Shale Composite (NASC), the clay minerals
are LREE-enriched (except Ce), whereas positive Ce
anomaly was observed in clays extracted from the A
horizon, and obvious negative Ce anomalies were exhi-
bited in clays from the lower parts of the profile, which
are pretty similar to those found in the corresponding
bulk samples (Fig. 9).
4. Discussion
4.1. Factors controlling the differentiation of REEs in
the weathering profile
In equilibrium with atmospheric CO2, meteoric water
is generally weakly acidic. Meteoric water percolating
through a layer of humus-rich topsoil could become
more acidic and corrosive and can carry a variety of
cations, including REE (Nesbitt, 1979). Organic acids,
including amino acids, fulvic acids, etc., have been
found to be abundant in the upper parts of the weath-
ering profiles developed on granitic rocks in South
China (Chen et al., 1997). Taunton et al. (2000)
demonstrated that microorganisms might accelerate the
dissolution of apatite and enhance the dissolution of pre-
formed secondary phosphates by changing the satura-
tion states through microbial uptake of phosphorous.
The organic acids can also lead to the decreased pH
values of percolating solutions in the profile. However,
to date, only a few metal-humate stability constants have
been determined experimentally (Viers et al., 1997).
They suggest that organic-REE complex play only a
minor role in REE leaching and migration during wea-
thering processes.
It is well known that cation adsorption onto clay
minerals is pH sensitive and cation specific. The ion
exchange capacity of certain cations in solution onto clay
minerals is related to its valence number, ionic radius,
and ion strength (Farrah and Pickering, 1979). In water-
clay systems, the fractionation of metal ions is due to the
differences in the relative affinities between the ions for
surface adsorption onto particles and for complexation to
ligand in solution (Cantrell and Byrne, 1987; Erel and
Morgan, 1991). Differences in the relative affinities of
REE are ultimately caused by a basic chemical property,
the lanthanide contraction, which is the systematic and
gradual trend in REE3+ stability constants which, in turn,
 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535 529

Fig. 6. Chondrite normalized and parent rock normalized REE patterns of the weathering materials from the four profiles. (A) and (B) REE patterns of
weathering crust developed on the Xinxiu granite, Longan County. (C) and (D) REE patterns of the weathering materials in profile developed on the
Huashan biotite granite (to diminish the zigzag effects in samples Hua95-1 and Hua-95-3 plots of Ho, Er, Tm, and Yb were deleted). (E) and (F) REE
patterns of the weathered materials developed on the Guposhan biotite granite. (G) and (H) REE patterns of the weathering materials in profile
developed on the Heling granite-porphyry Xunwu County. Chondrite-normalization values after Anders and Grevesse (1989).
530 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535

is interpreted as the result of the reaction between acidic

percolating solutions and feldspars in the profile.

2NaAlSi3 O8 þ 3H2 O ¼ Al2 Si2 O5 ðOHÞ4 þ 2Naþ

þ 2OH− þ 4SiO2 ðaqÞ

During the initial stage of weathering of granitoid,

REY released from the breakdown of accessory minerals
weakly resistant to weathering, such as doverite and
fergusonite and rock-forming minerals such as biotite
were probably accommodated by the secondary clay
minerals. As chemical weathering and erosion pro-
gresses, the REE were probably gradually released from
the breakdown of more resistant minerals and could be
taken up by the solutions, leading to migration and
accumulation within the profiles.
An experiment simulating the natural chemical
weathering of granite has been reported by Bao (1992),
in which 180 g of weathered material from the B horizon
of the Huashan profile filling a 40 cm column was
leached by 200 ml pH = 3 acidic water (HNO3) for 12 h.
Analyses of the products showed that the REE were
apparently mobilized and enriched in the lower part of
the column. Total (REE + Y) contents changed from
Fig. 7. REE fractionation in the weathering profiles in south China.
(LREE/HREE)s/p represents the LREE/HREE ratio of samples from 1000 ppm in the starting material to 543.1 ppm in upper
the profiles vs. those of the parent rocks. section and 1099 ppm in the lower section of the column.
Meanwhile, the LREE/HREE ratios changed from 8.3 in
the starting material to 14 in the upper part and 8.0 in the
results in LREE3+ being preferentially adsorbed to lower part of the column. Ce was also affected by the
surfaces and HREE3+ being retained in solution. This
causes the HREE to preferentially migrate and accumulate
in the deeper part of the weathering profiles. Avery limited
number of studies have been reported on coefficients for
the partition of REE between clay minerals and coexisting
aqueous solutions (Beall et al., 1979; Bruque et al., 1980).
Nevertheless, studies on river waters have shown that the
solution and colloidal phases are enriched in HREE and
LREE, respectively, and all aquifer types exhibit flat or
upwards-slopping Post-Archean Australian Shales
(PAAS)-normalized plots (e.g., Goldstein and Jacobson,
1988; Sholkovitz, 1992), suggesting that the LREE have
higher affinities to clays. Two active adsorptive centers,
i.e., the replacing structure and residual bond on the
fractured surface, are probably associated with cation
adsorption. Quantum chemical calculation (Chi et al.,
1995) based on this assumption shows that there exist
subtle differences among the REE3+. The order of REE
affinities to clay minerals is as follows: La 3+ N Ce 3+ N
Pr3+ N Nd3+ N Sm3+ N Eu3+ N Gd3+ N Tb3+ N Dy3+ N Ho3+ N
Y3+ N Er3+ N Tm3+ N Yb3+ N Lu3+.
This study has also shown that the abrasion pH
values decrease from 4.2 to 6.5 from the top to the bot- Fig. 8. Ce/Ce⁎ variation in the weathering profiles developed on the
tom of the weathering profile. The decrease of pH values Xinxiu, Huashan, Guposhan granites, and Heling granite-porphyry.
 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
Fig. 9. Chondrite-normalized (A) and NASC-normalized REE patterns of the clays in the weathering profile developed on the Heling granite-
porphyry (analyzed using INAA method).
percolating acidic solution. It behaved differently,
however, from other rare earths; the starting material
showed a negative Ce anomaly (Ce/Ce⁎ = 0.61), but after
the percolation a positive Ce anomaly was developed in
the upper part (Ce/Ce⁎ = 1.1) and the lower part of the
column became more Ce depleted (Ce/Ce⁎ = 0.60).
It was likely that the continuous leaching by acidic
meteoric water resulted in the removal of REE from the
clay minerals in the upper part of the column, accom-
panied by the transformation of clay minerals (kaolinite
to gibbsite) and re-adsorption of REE onto clay minerals
in the lower part of the weathering profile. Due to the
lower affinities of HREE to clay minerals, HREE are
more prone to preferential removal and enrichment at
lower parts of the studied profiles (Figs. 4–9) than the
LREE. After leaching and accumulation over tens to
hundreds of thousands of years, coupled with a low rate
of denudation (Huang et al., 1996; Harlavan and Erel,
2002), significant quantities of REE can be accumulated
in the subsurface part (B and C horizons) of the weath-
ering profiles; some can be of economic significance.
A small portion of the REE in the weathering profiles
might be hosted by secondary mineral phases, especially
in the A horizon. Unfortunately, due to technical diffi-
culties no investigation of the secondary REE-bearing
mineral phases in weathering profiles have been re-
ported in China. However, an extensive literature on
lateritic minerals hosting REE is available. They were
found to be present in very small crystals and aggregates
(b10 μm) and coexisted with clays and secondary Fe–Ti
oxides (Banfield and Eggleton, 1989; Taunton et al.,
2000). It is known, for instance, that Fe-hydroxides may
adsorb large quantities of REE; their co-precipitation
with Fe(OH)3 being even used as a pre-concentration
technique in analytical chemistry (e.g., Elderfield and
Greaves, 1982). Sequential acid-leaching experiments
531
on minerals and whole rocks of the Lueshe carbonatite
complex (D.R. Congo) show that the LREE distribu-
tions are controlled by Al-phosphates, whereas HREE
are controlled by both the residual minerals and the
REE-scavengers including Fe-hydroxides and probably
organic matters (Nasraoui et al., 2000).
4.2. Cerium anomalies in the weathering crusts
Cerium behaves differently from other REE during
chemical weathering processes. Positive Ce anomalies are
ubiquitous in the bulk samples and clay minerals within
the A horizon of the weathering profiles of granitic rocks
in South China (Figs. 4–9). In the Jigudong granitic
weathering profile from Xingning County, Guangdong
Province, Ce anomaly (Ce/Ce⁎) as high as 30 was found
in the lateritic horizon. Significant positive Ce anomalies
have also been reported in lateritic crusts from many other
places (e.g., Braun et al., 1990, 1998).
Due to its specific electron configuration (4f15d16s2),
cerium (Ce) occurs in nature as Ce3+[Xe]4f1 and Ce4+
[Xe]. Ce3+ can be oxidized to Ce4+ (Brookins, 1983;
Fig. 10) under oxidizing conditions. Ce+4, less soluble
than Ce+3, can be fixed in secondary minerals such as clay
minerals. Therefore, Ce behavior differs from other REE
that are exclusively trivalent, except for Eu. The existence
of Ce4+ in geological samples was observed for Ce-
enriched phases (Braun et al., 1990; Takahashi et al.,
2000a; Taunton et al., 2000). The actual ratio of Ce3+ and
Ce4+, determined by X-ray absorption near-edge structure
(XANES), was recently reported in natural samples of
(weathered) granitic rocks (Takahashi et al., 2000b). Both
Ce(III) and Ce(IV) species are found in weathered granite.
Ce(IV) was probably formed by oxidation in the
aqueous phase after being dissolved initially as Ce(III).
The dissolved fraction of REE along with Ce(III) could
532 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
Fig. 10. Eh–pH diagram for Ce at 25 °C and 1 bar pressure. Activities
of ions are: M2+, M3+, M4+, = 10− 6, Σ O2 = aH2CO3 + aHCO3− + aCO32− =
10− 3 (Brookins, 1983).
be removed from the weathering front by solutions.
However, the quick oxidation of Ce(III) to Ce(IV) make
it easily fixed onto clay minerals and/or Fe, Al oxides as
a result of oxidation, and thus removed from the solution
and migration process. Due to the low solubility and
high adsorptive activity of Ce(IV), and Ce is most likely
to occur as cerianite or adsorbed either as a monomeric
species or as a polymeric hydroxy cation to clays in the
weathering profiles, especially the upper part (Laufer
et al., 1984). Studies on waters confirm that all oxygen-
rich surface waters show variable but negative Ce
anomalies (Möller, 2002). Bau (1999) and Kawabe et al.
(1999) have shown experimentally that Ce anomalies
develop during aging of FeOOH precipitates. Microor-
ganism mediated microbial oxidation of Ce3+ might
contribute to the Ce anomaly formation in the top part of
the weathering profiles as was demonstrated to be
important in seawaters (Moffett, 1990). The oxidation to
Ce4+ and preferentially sorption onto oxyhydroxides
lead to the negative Ce anomaly in percolating meteoric
water, and accordingly, the striking Ce enrichment in the
A horizon and relative depletion of Ce in the subsurface
parts of the weathering profiles.
5. Summary
Mineralization of ion-exchangeable REY has been
found in weathering profiles of various rock types in
South China. The majority of the known rare earth
mineralization occurs, however, in the weathering
profiles of granitic rocks, especially Mesozoic granites.
Accessory minerals host most of the REY (N70%) in
the parent granitic rocks; rock-forming minerals host
generally b 30% REY. Thus, the resistances to
chemical weathering of the main REE-hosting acces-
sory minerals are important controls on the enrichment
of REY in the subsurface parts of the weathering
profiles.
Under warm and humid climate conditions, continual
leaching coupled with low rate of denudation resulted in
the REY depletion in the top layer (the A horizon) and
enrichment in subsurface layer (the B and C horizons) of
the well-developed layered weathering profiles of
granitic rocks. The acidic meteoric water percolation
can lead to differentiation of REE, i.e., the LREE/HREE
ratios decrease downwards in the profile. Most of the
REE and Y in the weathering profiles (except the A
horizon) are adsorbed onto clay minerals. Ion-exchange-
able REY can be replaced by cations like NH4+, Na+, K+,
etc. in electrolytes or removed by complexing agents
such as EDTA and EGTA. Cerium behaves differently
from other REE in the weathering profiles and results in
positive Ce anomalies in the A horizon. This is presum-
ably due to oxidation of Ce3+ to less soluble Ce4+ and
then formation of cerianite or absorption to Fe and Al
oxyhydroxides. In well-developed weathering profiles
of granitic rocks within which the major REY-bearing
accessory minerals are vulnerable to chemical weather-
ing economic accumulation of ion-exchangeable REY
can be achieved.
In conclusion, REE differentiation is common during
chemical weathering processes and has resulted in large
amount of REE accumulations in the subsurface
horizons of weathering profiles. Caution must be taken
in the application of REE geochemistry to sedimentary
provenance study.
Acknowledgements
This study is financially supported by NFSC (40472032,
40672070) and Guangzhou Institute of Geochemistry, CAS
(GIGCX-04-01). We are most grateful to the Longnan and
Heling REE corporations for access to the deposits and for
assistance during field sampling. Professors Yuzhuo Qiu,
Yixian Wang, Chuanxian Lin, and Zhixin Qian are thanked
for their advice and assistance with the laboratory work.
Professors Peter Möller and David Alderton and Ore
Geology Reviews Editor Nigel Cook provided constructive
reviews and comments that substantially improved the
manuscript. Professor Jayanta Guha, University of Quebec
at Chicoutimi, and Dr. Ren Shuangqui, Mineral Securities,
Australia, are thanked for their efforts to improve the written
style of this article.
 Z. Bao, Z. Zhao / Ore Geology Reviews 33 (2008) 519–535
Appendix A. Methods and procedures for REE analysis
REE concentrations of the samples were analyzed
using ion-exchange separation and ICP-AES or X-ray
fluorescence methods. Analytical errors for the elements
of higher concentrations are better than 5%, whereas for
those with lower concentrations are better than 15%. The
procedures of the methods are briefly described as follows.
(1) ICP-AES method: Samples of approx. 100 to
200 mg were dissolved with ∼2 g Na2O2 in
corundum crucibles under 700 °C for 15 min and
extracted with 75 ml 10% triethanolamine solu-
tion. A small piece of paper pulp was added and
the solution was boiled a while. 2 ml H2O2 solu-
tion was added after the solutions cooled down to
room temperature. The precipitates were then
filtered and rinsed 5 times with 2% triethanola-
mine and 2% NaOH solution, and twice with warm
distilled water. The precipitates were redissolved
using 10∼15 ml hot HCl and then concentrated to
about 1 ml, diluted to 4–5 ml with distilled water.
A small amount of ascorbic acid was added, as was
one droplet of thymolsulfonphthalein. The solu-
tions were neutralized with NH3H2O until they
turned yellowish and chloroactic acid-sodium
acetate buffer solution (pH = 2.4) was added to
dilute the solutions to 10 ml. The solutions were
then transferred onto ion-exchange columns, im-
purities were removed with 20 ml 2 molar HCl
solution, and REE were retrieved with 20 ml 4
molar HCl solution, and concentrated to 5 ml and
determined using JY-38 ICP-AES.
(2) X-ray fluorescence spectrography: Samples of 100
to 200 mg are dissolved in HF and H2SO4 solution
in gold bowls, extra H2SO4 solution is added to
expel HF. HCl is used to extract the solute, which
is then filtered and the solutions are adjusted to 2
molar HCl acidity. After running through ion-
exchange columns following the procedures
described for the ICP-AES methods, the solutions
were evaporated to about one droplet and diluted
to 15 ml (pH = 1.5–2). An ion-exchange mem-
brane was used to extract REE in the solutions,
rinsed with distilled water, dried and flattened for
X-ray fluorescence determination (Philips-1540).
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