Physics and Chemistry of the Earth xxx (xxxx) xxx

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Physics and Chemistry of the Earth

journal homepage: http://www.elsevier.com/locate/pce

Mineralogy and BCR sequential leaching of ion-adsorption type REE: A

novelty study at Johor, Malaysia
S.Z. Tohar a, M.Y. Mohd Yunus b, *
a
Faculty of Chemical and Process Engineering Technology, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300, Kuantan Pahang, Malaysia
b
Earth Resources and Sustainability Center (ERAS), Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300, Kuantan Pahang, Malaysia

A B S T R A C T

Since year 2010, advance research in resource investigation, mineralogy and geochemistry, environmental impact as well as processing technique of ion-adsorption
type rare earth elements (REE) deposit particularly in mining industry has been conducted worldwide. Ion-adsorption type REEs are formed by weathering process of
igneous rocks (typically granites) that contain certain REE-bearing minerals. Effect of the rapidly weathering, REE minerals are decomposed, and ionized REEs are
absorbed on clay minerals such as kaolinite and halloysite. A research study has been made in discovery the ion-adsorption type REE prospecting in Johor, Southern
Peninsular Malaysia with three vertical weathering profiles (up to 11 m) sampled on Besar island, Tengah island and Hujung island. Parent granite is A-type consist of
quartz, K-feldspar, plagioclase, biotite and 0.6–1.4 wt% accessory minerals (zircon, apatite, monazite-(Ce) and chlorite). The main REE-bearing minerals are
monazite-(Ce), apatite, zircon, titanite, allanite-(Ce) and bastnaesite-(Ce). Total REE concentrations in raw saprolite (potential REE horizon in weathering profiles) is
ranging between 1167 and 2339 ppm. The laboratory leach ability of the REE in different parts of the A-type granite weathering profiles was determined by carrying
out a three step BCR sequential extraction procedures. The evidence from the three-step BCR-701 (certified freshwater sediment standard) sequential extraction
procedure for ion-adsorption was consistent with a near instant process (≤1 h) with 70–80% recovery rate. This is due to the re-precipitation of REE3+ ions in solution
and due to hydrolysis of ions on the clay surface. The ion-adsorption (leached) fraction was enriched in light rare earth elements (LREE) compared with the raw
sample compositions of the saprolites and saprocks (Ce/Ce* ratio range largely from 0.17 to 0.82). The LREE accounted for 80–90% of the total REE content in the
investigated saprolite and saprock; allowed in agreement with the trend that was observed in Thailand and South China ores.

1. Introduction
Rare earth elements (REE) are a collection of seventeen chemical
elements in the periodic table, namely the fifteen lanthanides, plus
scandium and yttrium as defined by International Union of Pure and
Applied Chemistry (IUPAC). The REEs have been entirely classed as
“critical metals” in the United States (U.S. Geological Survey, 2015) and
also Europe (Sanematsu and Watanabe, 2016) corresponding to China
dominancy for supplying ~99% of Heavy Rare Earth Elements (HREE)
and 87% of Light Rare Earth Elements (LREE) respectively (Judith and
Shaw, 2011). The main industrial applications of REEs consists of strong
permanent magnets, lasers, superconductors and in catalytic converters
(Moldoveanu and Papangelakis, 2012). The present-day quantity of
consumed resources is totally different from the earlier 20 year times
(Sanematsu et al., 2013). Therefore, it is very difficult to secure and to
maintain the REE resources with the same capacity. These factors in­
crease the urgency to identify alternative REE resources (Sanematsu and
Watanabe, 2016). Most of the world’s supply of REE especially in HREE
comes from weathered crust elution-deposited or so-called ion adsorp­
tion deposits because the HREE generally occur with Y in their
geochemical bonding, and they have been mined predominantly from
ion adsorption-type REE deposits in southern China (U.S. Geological
Survey, 2015; Yaraghi et al., 2020). These deposits were formed by in
situ lateritic weathering of REE rich felsic rocks (mainly granites), which
led to the formation of weathered profiles containing residual REE-clays
(Ishihara et al., 2008). The ion-adsorption type deposits are composed of
reddish soil-like weathering crust developed on parent granite with the
upper part of the weathered granite is lower in REE (89–398 ppm) than
the middle to lower parts (201–1131 ppm); although the REE grades also
depend on those of the parent granite (Bao and Zhao, 2008). Additional
REE weathered crust elution-deposited or ion adsorption deposits oc­
currences have been discovered outside of China especially in Brazil
(Rocha et al., 2013), Malawi, Madagascar (Le Couteur, 2011), and
Southeast Asia (Sanematsu et al., 2013). The ion-adsorption type pros­
pects in Southeast Asia have been identified recently in Thailand,
northern Vietnam, Laos and southern Myanmar (Sanematsu and Wata­
nabe, 2016) owing to the tropical climate in Southeast Asia promotes
weathering process in a similar way as in southern China. The
ion-adsorption deposit is different between other conventional REE
deposit especially in their main bearing minerals (Sanematsu and

* Corresponding author.
E-mail address: yusri@ump.edu.my (M.Y.M. Yunus).

https://doi.org/10.1016/j.pce.2020.102947
Received 28 December 2019; Received in revised form 12 October 2020; Accepted 15 October 2020
Available online 17 October 2020
1474-7065/© 2020 Elsevier Ltd. All rights reserved.

Please cite this article as: S.Z. Tohar, M.Y. Mohd Yunus, Physics and Chemistry of the Earth, https://doi.org/10.1016/j.pce.2020.102947
S.Z. Tohar and M.Y.M. Yunus
Watanabe, 2016). The conventional REE deposit mainly from mon­
azite-(Ce) and xenotime-(Y) (Wall, 2014; Bao and Zhao 2008) whereas
ion-adsorption mainly from bearing minerals such as clay minerals and
bastnaesite (Sanematsu et al., 2013). This study describes and discusses
the geochemical and mineralogical characteristics of the ion adsorption
type REE mineralization in weathered granite at Besar Granite Group,
Peninsular Malaysia and general modelling on sequential extraction
leaching.
2. Granite in Besar Group
In Southeast Asia, granites are distributed into: (i) Western (south­
west Thailand–east Myanmar) provinces, (ii) Eastern provinces (east
Malaysia), (iii) Main Range provinces (south Thailand – west of Penin­
sular Malaysia) and (iv) Northern provinces (Thailand) (Hutchison,
1977; Cobbing et al., 1992). Two of the provinces were exposed in
Peninsular Malaysia; the Eastern and Main Range provinces. Both
provinces also known as Eastern and Western Belt granites (Fig. 1). High
SiO2 granites for both provinces are usually found in veins and
high-level dykes (Ghani A.A 2009). However, in unusual cases, the high
SiO2 granite can occur as small plutons characterized by homogeneous,
Fig. 1. Granite plutons of the Peninsula Malaysia, compiled from Cobbing et al. (1986) and Searle et al. (2012).
2
Physics and Chemistry of the Earth xxx (xxxx) xxx
enclave-free, and leucocratic rock (Ghani et al., 2014).
This type of high SiO2 granite pluton can be found at the Besar
granite group. The granite is exposed in three islands; Besar, Tengah,
and Hujung. Regionally, the Besar granite group islands expose the
easternmost plutonic and volcanic rocks of peninsular Malaysia as well
as many other islands such as Aur, Tioman, Pemanggil, Tinggi and Sibu
island (Ghani et al., 2014). The archipelago is gazette as a National Park
(Khoo 1974; Cobbing et al., 1992). A selection of igneous rocks are
exposed on these Islands, variation from basic to felsic plutonic rock and
pyroclastic to felsic and intermediate volcanic lava (Ghani and Azmi
2008). The age of the plutonic and volcanic rocks in the islands is poorly
known (Ghani et al., 2014) but from previous studies on biotite feldspar
granites from nearby island (Tioman), the granite is a zircon age of 80 ±
1 mega annum (Ma) (Searle et al., 2012). This study was conducted in
Besar group islands (Fig. 2), situated approximately 13 km off the
peninsular Malaysia mainland with total area of granitic rocks is about 4
km2 with ultrafelsic granite average of SiO2 content ~76.15% and high
K-feldspar + quartz content ~>70% (Ghani et al., 2014). The exhibit
petrographic, geochemical and tectonic signatures of this granite allow
them to be classified as A-type granites. They are also alkali-rich and
have high Rb, Nb, Ba, and REE + Y and +Ce contents (Ghani et al.,
S.Z. Tohar and M.Y.M. Yunus Physics and Chemistry of the Earth xxx (xxxx) xxx

Fig. 2. Geological map showing the distribution of granites on Besar islands Group. Modified after Ghani et al. (2014).

2013).
3. Weathering profiles
There were nine weathered granite samples and three parent granite
samples collected which covering Besar, Tengah and Hujung Island. The
weathering profile is divided into soil, saprolite, weathered rock (sap­
rock) and parent granite horizons from the surface to the bottom (Fig. 3).
The upper profile consists of dark brown soil with a thickness from 0.2 to
1 m, and from each location one sample was collected from this layer. It
is enriched in organic matters, clay minerals, and quartz and containing
small amounts of rock-forming minerals. The saprolite layers consists of
clay-rich with average 2.0–4.5 m thick with lesser amounts of organic
matters, showing yellowish and reddish brown color. Three samples
were collected from this horizon. The granitic texture is hardly recog­
nized by the naked eye in this layer. The weathered rock (saprock) is a
weathering crust on the parent granite, showing yellowish or dark grey
color. One sample was collected from this layer for each location of 2–3
m thickness. The fragments of granitic texture and rock-forming min­
erals such as feldspars and biotite are recognized by the naked eye. Clay

Fig. 3. Schematic columnar section of the studied weathering profile on (a) Besar island, (b) Tengah island, and (c) Hujung island. (PBSOIL, PTSOIL,PHSOIL – soil
layer; PBS, PTS, PHS – saprolite layer; PBW, PTW, PHW – saprock layer; PBF, PTF, PHF – parent granite).

3
S.Z. Tohar and M.Y.M. Yunus
minerals consist mainly of kaolinite with small amounts of halloysite,
illite and mineral assemblage not very different from the saprolite layer.
The saprock gradually changes to the saprolite without clear boundary.
Kaolinite and halloysite are common clay minerals in these layers. The
parent granite was found in the bottom layer of each weathering
profiles.
4. Analytical method
4.1. Chemical and mineralogical analyses
The parent granite sample were prepared as thin section for Meiji
MT9900 Transmitted and Reflected Light Microscopy Microscopy
analysis. Dried soil, saprolite and jaw-crushed weathered and parent
granite were ground in an agate laboratory disc mill (Sanematsu et al.,
2013). The major elements of the powered samples were analyzed by
using the X-ray fluorescence (Bruker S4 Pioneer) and trace elements
were analyzed by using inductively coupled plasma mass spectrometry
(ICP-MS) brand Agilent 7500a at Universiti Malaysia Pahang. The pol­
ished samples were observed by using the JEOL JSM-5400LV scanning
electron microscope (SEM) and major rock-forming minerals and
alteration minerals were identified using the X-ray diffraction (Siemens
D5000) with Material Data Inc. (Data Scan®, version 5) software at
Camborne School of Mines, United Kingdom. The analysis was carried
out using CuKα radiation, an accelerating voltage of 40 kV and a beam
current of 150 mA. The scan range (2θ) was from 3◦ to 60◦ with scan step
of 0.02◦ and scan speed of 2◦ /min. Qualitative and quantitative analyses
were performed by using analytical Functions: Oxford ISIS EDS system.
4.2. Sequential leaching procedure
The leaching procedure was performed to determine REE concen­
trations in each fraction. The BCR Sequential Leaching Method with
three-step sequential leaching procedure is use in this study. The reacted
materials at each step are assumed to be ion-adsorption (including ion-
exchangeable) materials in step 1, Mn and Fe oxides in step 2 and
organic matter and sulfides in step 3. The extraction procedure was
basically performed in conformity to the BCR procedure proposed by
Ure et al. (1993), Thomas et al. (1994) and Rauret et al. (1999). Before
beginning the procedure, all the centrifugal tubes, containers and flasks
were cleaned by soaking in 1 M HNO3 over 24 h and rinsed repeatedly
with distilled water before they were used. The step 1 extraction intends
to extract elements adsorbed on inorganic and organic materials and
exchangeable elements in clays and carbonates (Sanematsu et al., 2013).
A 40-ml volume of 0.5 M ammonium sulfate solution (adjusted at pH = 4
with H2SO4) was added to 1 g of powdered sample in a 50-ml centrifuge
tube and reacted with the sample by mechanical shaking for 1 h at room
temperature. The extract is separated from the solid residue by centri­
fugation for 20 min. The supernatant solution was filtered by using a
cellulose acetate-type membrane filter (ϕ = 0.22 μm), and the mem­
brane filter was repeatedly rinsed with 50 ml of distilled water. The
filtered solution was acidified using HNO3 and was kept in a poly­
propylene container. The mass of the solid residue on the filter was
measured for the next step 2 extraction because a small amount of res­
idue was lost during filtration. The step 2 proposes to extract elements
bound to the structures of Mn and Fe oxides by the change of redox
conditions. 40 ml of 0.5 M hydroxylammonium chloride (adjusted to pH
= 2 with HNO3) was added to the solid residue from the step 1. The
shaking, centrifuging and extraction procedures were repeated in the
same way as in step 1 (Sanematsu et al., 2013). The mass of the solid
residue on the filter was measured for step 3. The step 3 extraction was
performed to extract elements bound to organic matter, sulfur and sul­
fides. To extract the elements, a 20 ml of 8.8 M hydrogen peroxide was
added slowly to the residue from step 2. The residue was decomposed by
heating at 85 ◦ C on an oven or water bath and dried for 24 h. Forty
milliliters of 1 M ammonium acetate was added to the moist residue in
4
Physics and Chemistry of the Earth xxx (xxxx) xxx
the centrifugal tube. The shaking, centrifuging and extraction proced­
ures were repeated in the same way as in step 1. The concentrations of
REE were determined using the ICP-MS.
5. REE-bearing minerals in granite and weathered profiles
The REE bearing minerals observed in the parent granite of Besar
group in this three islands are made up mainly by monazite-(Ce),
allanite-(Ce), apatite and zircon. Monazite-(Ce) occur as colourless
grains, anhedral to subhedral, frequently associated with biotite and
zircon (Fig. 4). According to Udayakumar et al. (2020) and Hoshino
et al. (2016), monazite-(Ce) is a stable bearing REE mineral in unaltered
granites, hydrothermal deposits and the weathering environment. In
granites from Besar Group, it forms grains of about 15–100 μm in
diameter, is pale yellow and has high birefringence and high relief and
in weathered granite profiles (saprock and saprolite), some mon­
azite-(Ce) appears to have been unstable as it shows ragged outlines
and/or looks disaggregated cause from hydrothermal alteration
(Fig. 4a). This is due to weathering processes (Hoshino et al., 2016).
Apatite can be euhedral and stubby, acicular or lozenge-shaped (Fig. 4c).
Fig. 4d show a subhedral tabular biotite mineral containing apatite in­
clusions. In the same granite samples, single crystals and aggregates of
apatite were commonly found in association with zircon and mon­
azite-(Ce) (Fig. 5b). The estimated relative weathering rates of accessary
minerals on granite and weathering samples, are: zircon > allanite-(Ce)
> apatite > titanite (Harlavan and Erel, 2002). These indicate, in
weathering granite profiles of Besar Group, apatite is less resistant to
weathering than zircon. When apatite is altered due to weathering, it
can be replaced by secondary phosphates such as mineral rhabdophane
(chemical formula) and florencite (chemical formula) or can be dis­
solved. In saprolite samples of Besar Groups, the main REE bearing
minerals was from fluorocarbonate group such as basnaesite-(Ce) and
synchysite-(Ce) and apatite and their associated with clay minerals such
as kaolinite (Fig. 5d, e, f). Repreciptated apatite can often be found on
the surfaces of clay mineral such as kaolinite (Fig. 5d). The pitted apatite
surfaces morphology with kaolinite minerals is generally associated
with a proximity to the hydrothermal alteration (Sanematsu et al.,
2013). The alteration of minerals in granites may be an important means
of opening up grain boundaries to fluids (Jamtveit et al., 2008) and may
be primarily responsible for the dissolution of apatite (Oelkers et al.,
2008). In weathering profiles, euhedral to anhedral fine-grained REE
mineral bastnaesite (<10 μm) occur in cavities and along grain bound­
aries of kaolinite (Fig. 5e). The occurrence of bastnaesite suggests that it
crystallized in the process of deuteric alteration of the granite. Deuteric
alteration is a textural and mineralogical changes occur during the final
crystallization stages of the molten igneous rock.
6. Geochemistry of REE in weathered granite
The degree of chemical weathering of granitic rocks is represented by
the chemical index of alteration (CIA) proposed by Nesbitt and Young
(1982). The CIA values are mostly over 94% in the upper part of the
profile (soil layer) and less than 92% in the lower part (saprolite)
(Table 1). Because illite and kaolin group minerals (kaolinite and hal­
loysite) have CIA values of 75–85% and 100%, respectively, the upper
part and lower part of the profile are interpreted as kaolin alteration and
kaolin-illite alteration, respectively. The CIA values are consistent with
occurrences of alteration minerals identified. Generally, the weathered
profiles show a higher concentration of total REE compared to their
parent rocks as reported by Maulana et al. (2016). This result indicates
that weathered crusts were enriched in REE, consistent with enrichment
of REE in weathered granitic crusts reported from many areas (Ishihara
∑
et al., 2008; Imai et al., 2013). Total REE ( REE) contents of weathered
granite (saprock and saprolite) range widely from 365 to 2339 ppm. The
saprock is depleted in REE (365–624 ppm) whereas the saprolite mostly
enriched in REE (1167–2339 ppm) relative to the parent granite
S.Z. Tohar and M.Y.M. Yunus Physics and Chemistry of the Earth xxx (xxxx) xxx

Fig. 4. Photomicrograph of the granitic rocks from the Besar, Tengah and Hujung islands. (a) disaggregated monazite-(Ce); (b) quartz dissolution associated with
biotite and zircon; (c) Inclusion of allanite-(ce), apatite and zircon in biotite; (d) Acicular or lozenge-shape apatite in biotite minerals.

Fig. 5. SEM-backscattered electron images showing; (a) monazite-(ce) minerals in Besar island granite; (b) REE bearing minerals zircon and apatite associated with
biotite in Tengah island granite sample; (c) euhedral of allanite-(Ce) and zircon in Hujung island granite sample; (d) sheeted-like shapes of kaolinite minerals
associated with apatite in Besar island saprolite sample; (e) basnaesite-(ce) attached with altered kaolinite minerals in Tengah island saprolite sample; (f) REE-
flourocarbonate minerals, synchysite-(ce) with kaolinite and fluorite minerals in Hujung island saprolite.

(378–605 ppm) in Table 1. The soil layer represents a positive Ce
anomaly with calculation Ce/Ce* = CeN/(LaN × PrN)1/2, Eu/Eu*
EuN/(SmN × GdN)1/2 (N is normalized by chondrite (Sun and McDo­
nough, 1989)). The Ce anomaly of soil layer is (Ce/Ce* = 1.58–3.37)
whereas the saprolite shows a negative anomaly (Ce/Ce* = 0.17–0.22).
REE are mostly present in the ion-adsorption fraction of extraction step
1. The concentrations of extracted LREE and HREE from each fraction
are listed in Table 2, and chondrite-normalized REE patterns are illus­
trated in Fig. 6. The ion adsorption fraction is characterized by a nega­
tive Ce anomaly for all saprolite samples. La/Yb ratios of saprolite in
step 1 sequential extraction range from 23.9 to 35.2 unit? and suggest
that the saprolite tends to be enriched in LREE compared with the parent

5
S.Z. Tohar and M.Y.M. Yunus Physics and Chemistry of the Earth xxx (xxxx) xxx

Table 1
Major elements of whole rock analysis with total CIA chemical index of alteration determined by molecular proportion of [Al2O3/(Al2O3+CaO + Na2O + K2O)] ×
100, where CaO is not from carbonate (Nesbitt and Young 1982).
Sample PBF PTF PHF PBW PTW PHW PBS PTS PHS PBSOIL PTSOIL PHSOIL

type Parent Parent Parent Saprock Saprock Saprock Saprolite Saprolite Saprolite Soil Soil Soil
SiO2 (wt.%) 77.73 76.89 76.15 74.05 74.11 72.49 70.16 70.05 70.01 66.54 68.91 69.28
Al2O3 12.77 12.18 13.36 16.22 17.33 16.22 20.17 22.05 24.17 27.84 18.15 24.36
Fe2O3 1.66 1.56 1.11 1.81 2.82 2.09 2.66 2.67 1.33 4.90 5.76 3.06
CaO 0.03 0.03 0.10 0.03 0.16 0.05 0.05 0.45 0.05 0.02 0.03 0.12
MgO 0.07 0.12 0.10 0.06 0.11 0.14 0.10 0.09 0.12 0.05 0.05 0.55
Na2O 3.02 2.14 3.22 0.21 0.15 0.55 0.04 0.00 0.14 0.00 0.01 0.88
K2O 3.91 4.70 4.86 3.64 3.11 2.86 2.36 2.80 2.60 0.33 0.17 0.85
TiO2 0.26 0.15 0.17 0.12 0.09 0.24 0.28 0.26 0.16 0.50 0.80 0.44
P2O5 0.02 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.03 0.05
MnO 0.02 0.03 0.05 0.01 0.01 0.06 0.02 0.01 0.03 0.01 0.02 0.04
Cr2O3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.00
BaO 0.01 0.04 0.02 0.08 0.05 0.04 0.02 0.00 0.03 0.01 0.01 0.04
LOI 1.20 2.14 0.56 2.89 1.75 5.71 3.45 1.83 1.95 0.12 5.16 1.09
Total (%) 100.69 99.99 99.70 99.13 99.69 100.46 99.31 100.21 100.60 100.33 99.11 100.76
CIA (%) 64.74 63.91 62.06 80.68 83.52 82.44 89.18 87.15 89.68 98.76 98.86 92.94
Co (ppm) 0.24 0.19 0.24 1.68 0.09 1.83 9.43 13.29 10.33 2.18 32.67 25.87
Ni 0.20 0.32 0.18 0.75 0.14 0.17 4.03 0.81 6.88 13.57 5.47 3.97
Cu 0.92 5.22 0.92 2.56 5.53 3.68 4.13 1.09 4.08 21.16 10.17 9.30
Zn 33.65 58.13 36.16 37.90 11.60 41.53 36.01 10.86 35.69 27.02 19.15 31.30
Ga 29.17 28.52 29.17 27.85 20.98 76.37 17.16 28.41 27.79 30.06 21.54 26.84
Rb 224.56 212.37 287.90 206.45 200.99 119.64 97.48 39.49 65.81 3.11 14.93 398.42
Sr 30.81 28.67 29.98 14.11 17.23 20.71 8.57 2.16 36.78 5.54 3.93 28.13
Sc 0.15 0.12 0.15 0.17 1.38 2.12 0.09 0.09 0.09 0.11 0.09 0.09
Y 100.01 83.10 91.61 60.93 49.90 116.09 228.11 255.00 388.03 3.21 4.87 28.06
Zr 86.15 116.94 186.72 218.18 121.50 191.03 132.08 178.11 216.57 138.30 60.79 90.60
Nb 31.77 21.05 45.61 28.51 18.18 27.26 31.11 73.92 24.77 35.61 24.01 23.73
Mo 2.68 2.02 2.09 2.12 1.28 2.64 3.06 1.83 2.90 3.29 1.91 1.56
In 0.26 0.39 0.23 0.22 0.24 0.29 0.19 0.11 0.32 0.00 0.06 0.30
Sn 3.78 24.00 9.11 8.72 4.76 6.84 8.26 17.56 10.19 5.66 4.25 29.50
Sb 0.21 0.69 0.36 0.43 0.49 0.82 0.62 0.53 0.31 0.61 0.33 0.84
Cs 5.11 4.35 4.95 2.60 2.30 3.32 3.40 3.65 1.43 0.22 0.96 30.38
Ba 695.32 744.37 667.89 487.71 559.46 572.55 147.95 106.77 116.71 9.63 12.40 366.81
La 47.73 73.91 91.60 89.90 89.10 127.97 298.77 606.88 655.20 18.35 13.02 30.11
Ce 92.42 120.91 231.15 134.96 101.90 112.12 119.90 197.78 284.90 51.37 68.15 73.76
Pr 12.21 18.92 22.26 17.83 17.41 25.97 89.79 131.61 141.64 3.45 1.88 3.17
Nd 47.80 59.04 85.81 65.57 60.27 96.78 243.34 487.95 517.17 4.75 4.42 11.20
Sm 11.68 18.51 19.98 11.82 14.96 24.90 56.31 96.93 99.62 0.85 1.00 3.38
Eu 0.79 1.20 2.18 0.95 1.10 1.90 2.90 8.95 8.12 0.20 0.14 0.14
Gd 16.13 15.24 21.81 10.34 9.42 46.32 39.83 79.00 84.26 0.61 0.84 5.45
Tb 3.49 1.98 4.97 2.62 1.49 6.56 5.72 11.64 14.00 0.08 0.19 0.87
Dy 19.21 13.91 16.91 11.89 8.39 29.79 29.60 48.90 60.50 0.60 0.90 5.24
Ho 4.31 2.91 3.95 2.75 1.54 5.42 7.52 13.30 14.20 0.12 0.18 1.03
Er 9.94 8.27 7.28 5.45 4.40 11.90 19.91 23.93 35.35 0.37 0.54 3.00
Tm 3.27 0.98 0.79 0.90 0.66 2.73 3.35 3.51 7.14 0.06 0.08 0.45
Yb 7.59 6.74 4.90 3.98 4.22 13.33 19.21 18.65 24.57 0.49 0.61 2.98
Lu 1.51 0.94 0.59 0.56 0.64 2.92 3.62 3.60 5.20 0.09 0.10 0.47
Hf 4.53 5.01 5.73 8.53 4.74 3.41 9.11 12.07 2.51 4.27 2.15 3.53
Ta 4.18 7.45 3.29 3.85 2.34 6.31 7.34 13.94 3.27 6.98 4.69 5.77
W 3.10 4.72 3.11 2.73 2.47 4.87 18.18 115.04 82.61 10.26 201.16 97.45
Pb 25.37 21.69 33.82 15.49 9.05 32.12 19.51 19.29 22.76 4.50 7.65 43.84
Th 15.12 18.26 11.02 16.99 9.86 10.23 12.60 6.31 9.55 5.74 11.72 8.14
U 2.67 3.73 2.13 0.55 2.01 2.89 2.84 4.63 1.76 1.48 2.57 1.71
LREE 228.75 307.73 474.79 331.37 294.16 435.96 850.84 1609.09 1790.90 79.58 89.45 127.21
HREE 149.32 118.84 131.00 89.08 71.24 188.74 317.04 378.53 548.99 5.02 7.47 42.10
∑
REE 378.08 426.57 605.79 420.46 365.41 624.69 1167.88 1987.62 2339.90 84.60 96.92 169.31
La/Yb 6.29 10.96 18.69 22.60 21.12 9.60 15.55 32.54 26.67 37.45 21.34 10.10
Ce/Ce* 0.938567 0.792751 1.255071 0.826483 0.63437 0.476845 0.179482 0.171582 0.229295 1.582948 3.377272 1.85106

granite. A minor REE-bearing fraction is derived from Mn and Fe oxides 7. Discussion

at extraction step 2 and percentages of extracted REE relative to raw
saprolite REE range from 13% to 40% in all samples. Small amounts of
REE are present in organic matter and the sulfide fraction of extraction
step 3, and the percentage of extracted REE relative to whole-rock REE
ranges from 1% to 10% in all samples (Table 2). These results indicate
that adsorbed REE are dominant in abundance in most of the saprolite
samples compared with REE present in Mn and Fe oxides, organic matter
and sulfides.
The difference in REE contents of the weathered granite samples was
explained by seeking of mobile elements from the weathering profile
and transportation of REE from the upper part to the lower part of the
profile (Nesbitt 1979). All samples in the weathering profile (saprolite
and saprock) are depleted in mobile major elements of alkali elements
and alkaline earth elements. Most of the samples are weakly depleted in
Si and strongly depleted in Fe and Ti suggests that saprolite may contain
large amounts of clay minerals related to hydrothermal activity
(Table 1). The enrichment of LREE relative to HREE is a common feature
of granite weathering profiles (Compton et al., 2003; Laveuf and Cornu,

6
 S.Z. Tohar and M.Y.M. Yunus
Table 2
Results of sequential extraction of REE from weathered granite and parent granite.
Sample Extraction La Ce Pr Nd Sm Eu Gd Tb Dy Ho Y Er Tm Yb Lu Total REE La/Yb

(ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm)

PBF Step 1 3.20 6.54 0.77 3.40 0.88 0.04 1.46 0.34 1.66 0.35 10.80 0.89 0.11 0.61 0.08 31.13 5.23
Step 2 31.68 60.25 7.60 33.42 8.20 0.36 12.24 2.26 14.15 2.71 69.13 6.96 0.83 4.37 0.54 254.73 7.25
Step 3 7.04 12.75 1.67 6.76 1.77 0.09 2.11 0.45 2.77 0.62 14.18 1.70 0.27 1.50 0.22 53.91 4.70
Step 4 4.81 11.88 1.17 1.23 0.21 0.30 0.31 0.44 0.62 0.63 5.72 0.11 0.06 0.11 0.26 27.86 45.04
PTF Step 1 6.86 3.46 0.89 3.76 0.81 0.06 0.95 0.12 0.73 0.14 4.10 0.36 0.04 0.26 0.04 22.59 26.21
Step 2 27.46 11.85 5.32 19.85 5.33 0.55 9.17 1.27 6.79 1.23 27.66 3.13 0.42 2.68 0.34 123.03 10.26
Step 3 39.14 20.16 11.61 23.54 3.28 0.32 4.72 0.57 2.92 0.54 15.59 1.20 0.14 0.91 0.15 124.80 42.81
Step 4 0.45 85.34 1.00 10.89 8.59 0.19 0.15 0.01 3.17 1.00 33.77 3.58 0.37 2.39 0.41 151.32 0.19
PHF Step 1 12.19 9.54 3.06 9.40 1.58 0.10 2.46 0.34 1.96 0.45 12.20 0.99 0.13 0.71 0.09 55.20 17.12
Step 2 50.35 40.40 11.35 49.06 11.42 0.86 11.91 1.68 8.32 1.32 31.63 2.96 0.32 1.75 0.22 223.56 28.78
Step 3 27.83 25.30 6.61 26.19 6.27 0.50 6.72 1.02 5.06 0.86 19.78 1.93 0.25 1.22 0.18 129.72 22.80
Step 4 0.73 154.90 0.24 0.65 0.03 0.52 0.11 0.93 0.26 0.83 27.50 1.36 0.10 0.22 0.01 188.37 3.35
PBW Step 1 57.47 4.22 12.07 32.33 6.31 0.29 6.54 1.03 5.13 0.92 24.70 1.95 0.18 1.02 0.15 154.31 56.17
Step 2 16.75 7.14 4.12 8.12 1.68 0.21 2.12 0.35 2.12 0.31 8.12 0.78 0.11 0.66 0.11 52.72 25.32
Step 3 2.99 5.17 0.72 3.12 0.72 0.08 0.88 0.14 0.72 0.14 4.12 0.38 0.05 0.32 0.05 19.60 9.40
Step 4 12.39 118.02 0.42 21.00 2.72 0.07 0.13 0.44 2.91 0.96 23.13 2.35 0.35 1.97 0.25 187.13 6.28
PTW Step 1 35.02 49.28 6.25 23.08 4.18 0.32 5.47 0.68 4.53 0.92 28.20 2.45 0.31 1.72 0.26 162.66 20.31
Step 2 7.88 35.84 1.57 6.10 1.07 0.09 0.89 0.10 0.64 0.11 3.16 0.27 0.03 0.21 0.03 57.99 36.82
Step 3 1.06 2.79 0.19 0.78 0.18 0.01 0.20 0.02 0.15 0.03 0.95 0.09 0.01 0.07 0.01 6.56 14.43
Step 4 45.15 13.39 9.40 30.32 9.07 0.68 2.79 0.68 3.07 0.47 17.27 1.60 0.31 2.21 0.34 136.73 20.45
PHW Step 1 106.85 2.16 16.78 71.95 14.94 0.93 17.84 2.69 15.02 3.32 81.00 6.99 1.05 5.83 0.79 348.13 18.33
Step 2 13.93 43.51 3.17 12.06 2.65 0.26 2.09 0.36 1.96 0.36 8.56 0.81 0.10 0.47 0.06 90.34 29.77
7

Step 3 6.44 0.29 1.41 4.34 0.97 0.08 1.03 0.17 0.89 0.15 3.50 0.31 0.03 0.15 0.02 19.79 42.62
Step 4 0.55 65.15 4.42 7.43 6.33 0.12 24.36 2.34 10.92 1.19 20.99 3.13 0.54 6.88 1.22 155.58 0.08
PBS Step 1 292.76 29.50 83.37 236.82 53.17 1.22 32.61 4.22 22.46 4.85 134.70 11.95 1.57 9.55 1.41 920.16 30.66
Step 2 1.50 25.04 0.64 2.36 0.42 0.03 0.71 0.07 0.29 0.06 1.62 0.13 0.02 0.14 0.03 33.06 10.66
Step 3 0.80 3.43 0.26 0.75 0.09 0.01 0.09 0.01 0.06 0.01 0.31 0.03 0.00 0.03 0.01 5.90 27.54
Step 4 3.71 60.93 5.52 0.40 2.63 1.64 5.92 0.92 6.78 2.60 89.50 7.50 1.75 9.49 2.18 201.48 0.39
PTS Step 1 481.41 62.72 122.65 417.25 87.78 4.18 70.00 7.26 38.70 8.30 213.00 18.93 2.51 13.65 1.60 1549.94 35.27
Step 2 13.86 120.66 4.96 20.26 4.84 0.41 4.16 0.69 3.74 0.73 14.51 2.00 0.31 1.79 0.30 193.22 7.73
Step 3 1.43 13.43 0.40 1.57 0.45 0.06 0.44 0.06 0.43 0.09 2.45 0.25 0.03 0.18 0.03 21.31 7.81
Step 4 108.18 0.97 2.60 48.37 0.86 3.31 2.40 3.25 5.83 0.18 25.37 2.75 0.65 3.02 0.67 208.41 35.78
PHS Step 1 445.04 32.62 128.88 452.27 83.39 3.00 72.26 9.00 50.50 11.20 307.00 23.35 3.14 18.57 2.20 1642.41 23.97
Step 2 15.71 53.85 4.10 18.29 8.20 0.32 8.11 1.24 6.48 1.20 23.95 2.13 0.32 1.99 0.34 146.21 7.89
Step 3 1.32 6.12 0.39 1.59 0.67 0.05 0.69 0.15 0.73 0.14 3.12 0.25 0.04 0.21 0.03 15.49 6.23
Step 4 192.13 188.31 6.26 44.02 5.36 1.75 1.21 1.61 1.79 0.66 51.84 5.61 0.65 0.80 0.63 502.65 240.94

Physics and Chemistry of the Earth xxx (xxxx) xxx

PBSOIL Step 1 8.21 18.33 0.73 2.41 0.44 0.17 0.28 0.04 0.30 0.11 1.87 0.20 0.02 0.17 0.03 33.30 49.46
Step 2 8.11 20.42 0.79 1.13 0.11 0.01 0.22 0.01 0.10 0.004 0.60 0.09 0.02 0.21 0.02 31.85 38.62
Step 3 0.03 0.07 0.01 0.02 0.01 0.01 0.004 0.001 0.01 0.001 0.05 0.01 0.002 0.01 0.002 0.23 2.48
Step 4 2.00 11.58 1.88 1.19 0.30 0.01 0.11 0.02 0.20 0.005 0.70 0.05 0.01 0.10 0.04 18.18 19.63
PTSOIL Step 1 6.92 30.88 0.64 2.11 0.60 0.04 0.22 0.09 0.45 0.07 2.09 0.28 0.03 0.19 0.01 44.62 36.44
Step 2 4.20 22.54 0.16 1.55 0.10 0.05 0.33 0.03 0.20 0.03 0.76 0.04 0.02 0.11 0.02 30.14 38.18
Step 3 0.06 0.20 0.04 0.05 0.02 0.002 0.02 0.01 0.04 0.01 0.25 0.04 0.01 0.05 0.04 0.84 1.20
Step 4 1.84 13.93 0.98 0.76 0.28 0.05 0.27 0.06 0.25 0.07 1.77 0.18 0.02 0.31 0.03 20.79 5.96
PHSOIL Step 1 9.32 30.88 1.41 4.80 1.89 0.07 2.55 0.21 0.51 0.43 11.76 1.20 0.22 1.64 0.25 67.14 5.68
Step 2 8.50 19.43 0.80 1.70 0.22 0.02 0.34 0.35 1.76 0.32 3.16 0.45 0.06 0.93 0.11 38.15 9.14
Step 3 1.19 1.54 0.21 0.66 0.05 0.01 0.04 0.03 0.08 0.03 0.88 0.03 0.01 0.03 0.01 4.79 47.60
Step 4 11.10 21.91 0.75 4.04 1.22 0.04 2.52 0.28 2.89 0.25 12.26 1.32 0.16 0.39 0.10 59.23 28.83
S.Z. Tohar and M.Y.M. Yunus
Fig. 6. Chondrite-normalized (McDonough and Sun, 1995) REE patterns for all saprolite sample types from Besar, Tengah and Hujung islands. The REE patterns of
each extraction step and the whole rock are individually shown.
2009; Sanematsu et al., 2013; Hoshino et al., 2016). However, the
fractionation of REE is not easily explained from whole-rock geochem­
ical data because it is controlled by the occurrence of REE-bearing
minerals, which have different LREE/HREE, and their varying resis­
tance to alteration. REE derived from the breakdown of phosphate and
most silicate phases are relatively enriched in LREE except zircon which
has a higher HREE/LREE and is particularly resistant to weathering
(Hoshino et al., 2016). It is for this reason that, in general, the saprolites,
which contain relatively low zircon, are relatively LREE-rich compared
with the parent and saprocks in the granite weathering profiles from
Besar Groups island (Fig. 7a). There is a significant result in saprolite
profiles for this three islands, where total REE percentage is considered
high and this may be a REE potential, but the patterns were variable and
weak. In addition to REE bearing minerals characteristic, the process of
ion adsorption tends to produce a relative enrichment in the LREE. This
is despite the results of experimental studies on saprolite profiles which
showed that LREE were easily adsorbed onto kaolinite relative to HREE
at high ionic strength and in low-pH solutions (Coppin et al., 2002). In
Besar island granite groups weathering profiles, however, the selective
adsorption of LREE is dominant, which may imply lower ionic strength
fluids and/or higher pH groundwater. The soil layer is depleted in REE
except for Ce whereas the lower profile which is saprolite tends to be
enriched in these elements. This result indicates that REE were
8
Physics and Chemistry of the Earth xxx (xxxx) xxx
transported from the saprolite (leached zone) and were immobilized in
the lower part of the saprock (accumulation zone) (Fig. 7b). Soil water in
the upper part of the profile is acidic because of abundant humic sub­
stances and atmospheric CO2 near the surface, leading to the alteration
of REE-bearing minerals. REE fluorocarbonate in the parent granite is
easily soluble in acidic soil water. Occurrences of REE fluorocarbonate
minerals were reported from parent granite of ion-adsorption type de­
posits (Ishihara et al., 2008). Bastnaesite-(Ce) in the parent granite is
easily soluble in acidic soil water as this accessory minerals are weakly
resistant to weathering (Bao and Zhao, 2008). In soil water, REE are
considered to be dissolved by forming carbonate complexes of REECO3+
and free ions of REE3+ (Wood, 1990). The REE complexes and REE3+ are
positively charged and are adsorbed onto negatively charged or zero
charge materials such as kaolinite. The point of zero charge of kaolinite
is less than 3.6 (Schroth and Sposito, 1997; Kosmulski, 2011), suggesting
that kaolinite is negatively charged in ion adsorption ores with low pH of
4.1–6.5 (Wei et al., 2001; Pan, 2011; Yang and Xiao, 2011) and thus is
capable of adsorbing REEs. Weathered granite contains various
adsorptive weathering products which may adsorb positively charged
REE complexes and ions. The adsorptive materials are considered clay
minerals such as kaolinite and halloysite and Al-hydroxyoxides in
ion-adsorption type REE deposits of southern China (Bao and Zhao,
2008). In the studied weathered granite of Besar Island Group samples,
S.Z. Tohar and M.Y.M. Yunus
Fig. 7. (a) Diagram of La/Yb ratio representing the fractionation of REE between. whole-rock and ion-adsorption fraction of the granite weathering profiles. (b)
whole-rock REE content and adsorbed REE concentration.
REE minerals commonly occur mainly with kaolinite and small amount
of halloysite. However, the adsorptive material was not easily identified
because of the difficulty in analyzing small amounts of REE distributed
on the surface of fine-grained weathering products and amorphous
materials. Therefore, REE adsorption in weathered granite is controlled
by the variety of adsorptive materials such as clays. Fig. 6 shows the
negative Ce anomaly of the step 1 leaching in saprolite is suggesting that
the Ce anomaly of weathered granite profiles may be an indicator of
ion-adsorption type REE mineralization.
8. Conclusion
The A-type granite in Besar Group is the parent rock of a weathering
profile with ion-adsorption type REE mineralization. Bastnaesite-(Ce) as
REE-bearing mineral, which occurs in cavities and cracks in feldspars, is
the most dominant REE source for the mineralization because it easily
dissolved in acidic soil water. The weathering profile on the parent
granite is divided into saprolite and saprock by the redox boundary near
2 m depth. The saprolite is a leached zone characterized by a negative Ce
anomaly with elevated REE contents (1167–2339 ppm) and high per­
centage adsorbed REE (38%–60%). The saprock layer is an accumula­
tion zone with negative Ce anomaly, REE contents (365–624 ppm) and
lower percentages of adsorbed REE (20%–40%). These results indicate
that the depletion and enrichment of REE resulted from transport of REE
from the upper part to the lower part of the profile. The positive Ce
anomaly in soil layer suggests fixation of Ce4+ under oxidizing and
acidic conditions, whereas the negative Ce anomaly and REE enrichment
in the lower part of the profile indicate the immobilization of REE3+ by
adsorption and distribution into secondary REE minerals. The results
showed that REE in the weathered profiles layer (saprock and saprolite)
are present in the ion-adsorption fraction with negative Ce anomaly,
there was a positive correlation between the percentages of adsorbed
REE and the whole rock negative Ce anomaly. Fractionation between
LREE and HREE by weathering is controlled by the occurrence of REE-
bearing minerals and adsorption by weathering products in weathered
9
Physics and Chemistry of the Earth xxx (xxxx) xxx
granite. The ion-adsorption fraction tends to be enriched in LREE rela­
tive to saprolite layer (weathered granite). Further detailed studies on
the occurrence of these critical metals (REE) in Peninsular Malaysia
should therefore be conducted intensively in order to maximize the
potential of these materials for the better development.
CRediT authorship contribution statement
S.Z. Tohar: Conceptualization, Methodology, Resources, Writing -
original draft. M.Y. Mohd Yunus: Writing - review & editing, Super­
vision, Validation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work was undertaken at Universiti Malaysia Pahang and Cam­
borne School of Mines, University of Exeter and was funded by Research
grant: RDU190160, Malaysian Ministry of Higher Education. We are
grateful to Professor Azman Ghani from Universiti Malaya for the sup­
port during the sample collection at Besar Group.
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