Gond. Geol. Mag., V. 29(1 and 2), June and December, 2014. pp.
Understanding the Behaviour of Rare Earth Elements in
Minerals and Rocks
Kirtikumar Randive1, *, J. Vijaya Kumar1, 2, Abhijeet Bhondwe1 and Shubhangi Lanjewar1
1
Post Graduate Department of Geology, RTM Nagpur University, Nagpur 440 001, India
2
Ore Dressing Division, Indian Bureau of Mines, Ajmer, Rajasthan, India
*E-mail: randive101@yahoo.co.in
ABSTRACT
Rare earth elements or lanthanides comprised a
series of elements between La (57) and Lu (71), show
remarkable similarity in their oxidation states (3+) and
chemical properties. The trivalent REEs show significant
substitution for Mn2+, Ca2+, Y3+, Th4+ and Zr4+; which greatly
influences their partitioning in various mineral phases,
such as plagioclase, allanite, apaptite, monazite and zircon.
The partitioning of REEs in mineral/melt systems had
been thoroughly investigated, and as such their partition
coefficients in different types of magma are now available.
Study of magmatic rocks provides valuation information on
their mantle source regions; viz. degrees of partial melting,
fractionation, heterogeneity, assimilation or contamination
and metasomatism. On the other hand, REEs do not
fractionate readily during sedimentation, nevertheless, a
remarkable uniformity is observed in the REE patterns
of sedimentary rocks. Weathering processes are however,
known to fractionate REEs. In case of metamorphic rocks,
the protolith composition and P-T-X conditions influence
distribution and mobility of REEs. Behavior of REEs
in Palaeogene-Neogene-Holocene systems depends on
the media being samples, e.g. volcanic rocks, pyroclastic
products mostly volcanic ash, wind-borne sediments and
alluvial soils. With the proper understanding of the system
being investigated, REEs may prove to be useful tracer of a
wide range of petrogenetic processes.
Keywords: : REE, Minerals, Rocks
INTRODUCTION
The Rare Earth Elements (REE), commonly
known as lanthanides, having atomic numbers ranging
from Lanthanum (La) 57 to Lutetium (Lu) 71. However,
Scandium (Sc) and Yttrium (Y) are also included in
the series. But Scandium which does not behave like
REE is not preferred in the series by geochemists. The
lanthanides have very similar geochemical properties
because they occur in 3+ ionic forms in nature. However,
Europium (Eu) also occur in 2+ (larger ion) and
Cerium (Ce) in 4+ (smaller ion) oxidation states. They
only differ in number of electrons in the 4f shell; this
shell has no involvement in forming chemical bonds,
therefore the elements have very similar chemical
properties. The major difference between REE is their
size, which decreases with increasing atomic number.
This variation is due to the increased nuclear charge,
which is only partially shielded by the 4f electrons; this
feature is also known as lanthanide contraction. Due
to size differences, REE can preferentially substitute in
different minerals. Though such difference is small, it has
a significant bearing on partitioning of REEs in different
minerals (Henderson, 1984; Boynton, 1989; Rollinson,
1993; Randive, 2012).
GENERAL CHARACTERISTICS OF
RARE EARTH ELEMENTS
Oxidation States
The REEs which are strongly electropositive, prefer ionic
over covalent bonding and during ionization, first electrons
to be removed are two from 6S, followed by 5d and 4f
sub-shells. All REEs show remarkably constant valence of
three. However, Eu and Yb can exist in 2+; whereas Ce and
Tb in 4+ oxidation states (Hendersen, 1984).
Oxygen Fugacity
The Eu2+/Eu3+ ratio is a good indicator of oxygen
fugacity prevailing during formation of minerals (Towell
et al., 1965; Phillpotts, 1970; Drake, 1975). The close
similarity in the ionic radii and charge of Sr2+ and Eu2+
would lead to almost identical partitioning behavior of
the two ions in the rock systems. This similarity could
be used to calculate the Eu2+/Eu3+ ratio, and hence the
oxygen fugacity in a system where the partitioning of
Eu2+ is significantly different from Eu3+ (Phillpotts, 1970).
For e.g. when two phases (Phase I and Phase II) are in
equilibrium, their europium concentration relationship
can be explained by following equations:
[Eu]Phase I = [Eu2+]Phase I + [Eu3+]Phase I
[Eu]Phase II = [Eu2+]Phase II + [Eu3+]Phase II
Thus,
[Eu]Phase II = D2+Phase II/Phase I ([Eu]Phase I [Eu3+]Phase I) +
D3+Phase II/Phase I[Eu3+]Phase I
174 Kirtikumar Randive and Others

Similarly, in minerals from six-fold to twelve-fold and even higher

[Eu3+] Phase I = ([Eu]Phase II D2+Phase II/Phase I[Eu]Phase I / (Hendersen, 1984). It is expected that the smaller REE ions
(D3+Phase II/Phase I D2+Phase II/Phase I)
Also,
[Eu2+]Phase I = [Eu]Phase I [Eu3+]Phase I
Where, Dn+Phase II/Phase I is the distribution coefficient value
for Sr between Phase II and Phase I.
This method has been applied successfully to
europium distribution amongst feldspar, pyroxene and
matrix phases of basalts, andesites and dacites (Phillpotts,
1970; Hendersen, 1984).
Element Coordination
The REEs occupy a wide variety of coordination polyhedron
occupy six-fold coordination sites, but the REE minerals
rarely show this coordination. On the contrary, they tend
to show greater coordination, such as seven-fold (sphene),
eight-fold (zircon), nine-fold (monazite), eleven-fold
(allanite), and twelve-fold (perovskite).
Ionic Radius
Comparison of the relative sizes of the REE ions with
those of other cations shows that there are few ions of
similar sizes. Na+ and Ca2+ have similar sizes (six-fold
coordination). Eu2+ has similar radius to that of Sr2+ (See
Table 1). K+, Rb+, Cs+ and Ba2+ are larger than trivalent
REE ions; whereas most of the transition elements are

Table 1: Ionic radius of rare earth elements in different coordination and possible substitutions (Data sources: Shannon,
1976; Hendersen, 1984; Burt, 1989).
S. Ion Coordination number and ionic radius
Common and Possible substitutions of REEs in minerals
No. 6-fold 7-fold 8-fold 9-fold 10-fold 12-fold
Rare Earth Elements (a) Simple Substitutions
1 La3+ 1.023 1.10 1.160 1.216 1.27 1.36 Eu2+Ca+-1 (Plagioclase)
2 Ce3+ 1.01 1.07 1.143 1.196 1.25 1.34 Ce4+Th4+-1 (Cerianite)
NaCeCa-2 (Apatite, Loparite)
3 Ce4+ 0.87 0.97 1.07 1.14
CaThCe-2 (Monazite, Britholite)
4 Pr3+ 0.99 1.126 1.179 (b) Substitutions with cation vacancies
5 Pr4+ 0.85 0.96 Ce2Ca-3 (Hellandite, Semenovite)
6 Nd2+ 1.29 1.35 Ce2(NaCa)-1 (Gagarinite)
7 Nd3+ 0.983 1.109 1.163 1.27 Ce4(Th3)-1 (Thorianite)
8 Sm2+ 1.22 1.27 1.32 (c) Coupled Substitutions
9 Sm3+ 0.958 1.02 1.079 1.132 1.24 CeNa(SrCa)-1 (Carbocernaite, Burbankite)
10 Eu2+ 1.17 1.20 1.25 1.30 1.35 YNb(FeW)-1 (Wolframite)
CeNb(UTi)-1 ( Branneraite)
11 Eu3+ 0.947 1.01 1.066 1.120
YTi(FeNb)-1 ( Columbite)
12 Gd3+ 0.938 1.00 1.053 1.107 CeTi(CaNb)-1 (Euxenite/Aeschynite, Pyrochlore)
13 Tb3+ 0.923 0.98 1.040 1.095 YFe3+(Fe2+Ti)-1 (Ilmenite)
14 Tb4+ 0.76 0.88 CeFe3+(CaTi)-1 (Perovskite, Titanite)
15 Dy2+ 1.07 1.13 1.19 CeMg(CaAl)-1 (Dollaseite)
16 Dy3+ 0.912 0.97 1.027 1.083 YP(CaS)-1 (Churchite-Gypsum)
17 Ho3+ 0.901 1.015 1.072 1.12 CeP2(KS2)-1 (Florencite-Alunite)
18 Er3+ 0.890 0.945 1.004 1.062 YP(ZrSi)-1 (Xenotime-Zircon)
CeNb(CaW)-1 (Scheelite)
19 Tm2+ 1.03 1.09
CeSi(CaP)-1 (Britholite)
20 Tm3+ 0.880 0.994 1.052 CeSi(ThB)-1 (Tritomite)
21 Yb2+ 1.02 1.08 1.14 CeAl(CaSi)-1 (Chukhrovite)
22 Yb3+ 0.868 0.925 0.985 1.042 YAl(MnSi)-1 Spessartine
23 Lu3+ 0.861 0.977 1.032 CeB(CaSi)-1 (Melanocerite, Tritomite)
Non-REEs having similar ionic radii Ce2B(Ca2P)-1 (Melanocerite)
YBe(CaB)-1 (Gadolinite-Homilite, Hingganite-Datolite)
24 Na+ 1.02 1.12 1.18 1.24 1.39
CeO(CaF)-1 (Fersmite, Pyrochlore, Apatite)
25 Ca2+ 1.00 1.06 1.12 1.18 1.23 1.34 CeO(CaOH)-1 (Hydroxylapatite)
26 Sr2+ 1.18 1.21 1.26 1.31 1.36 1.44 ThO(CeF)-1 (Ancylite, Hibonite)
27 Mn2+ 0.830* 0.90* 0.96 YOH(ZrO)-1 (Zircon)
28 Pb2+ 1.19 1.23 1.29 1.35 1.40 1.49 CeOH(CaH2O)-1 (Ancylite, Hibonite)
29 Y3+ 0.900 0.96 1.019 1.075 (d) Coupled substitutions involving vacancies
30 Th4+ 0.94 1.05 1.09 1.13 1.21 YF(Ca)-1 (Tveitite, Flurite)
31 U4+ 0.89 0.95 1.00 1.05 1.17 Y2(U2O)-1 (Uraninite)
Y2S(Pb2)-1 (Galena)
(e) Coupled substitutions involving change in valance
CeFe2+(CaFe3+)-1 (Allanite, Gadolinite)
Ce4+O(Ce3+OH)-1 (Metamict phases)
Symbol * indicates high-spin state only Stands for Vacancy
 Understanding the Behaviour of Rare Earth Elements
smaller, with the exception of Mn2+, Y3+, Th4+ and U4+
(Hendersen, 1984; Rollinson, 1993).
Substitution in Minerals
Ionic substitution plays an important role in governing the
substitution of trace elements (Goldschimdt, 1937). The
large ionic radii of REE preclude significant substitution
of these elements into minerals. substitution of trivalent
REE are observed for Ca2+, Y3+, Th4+, U4+, Mn2+ and Zr4+.
Due to large variation in ionic radii of REEs different
minerals provide selective substitution for them. For
e.g. apatite prefers LREEs whereas garnet preferentially
substitutes HREEs in their crystal structures. Common
exchange reactions for substitution include following:
R3+ + Al3+ + CaAl2Si2O8 RAl3SiO8 + Ca2++Si4+
R3+ + Na+ + 2CaAl2Si2O8 2C (R, Na) Al2Si2O8 + 2Ca2+
2R3+ + Ca5(PO4)3OH (R2 Ca2) (PO4)3OH + 3Ca2+
(Where symbol stands for Vacancy)
Partition
Onuma et al. (1968) and Jensen (1973) demonstrated
the influence of ionic radius and ionic charge on the
patitioning of elements in mineral/melt systems.
They plotted logD against ionic radius diagrams and
demonstrated that the ions having same charge show
fairly smooth curve, which is due to presence of Eu2+
along with Eu3+. Therefore, these minerals having larger
Fig.1. Diagrams showing partitioning of Rare Earth Elements (REEs) in different minerals in (a) Basaltic melt, (b) Andesitic melt, and
(c) Rhyolitic melt (data from Rollinson, 1993 and references therein).
175
coordination polyhedron (e.g. allanite) favor larger
ions (LREE), while those having relatively smaller
polyhedron (e.g. zircon) favor HREE.
Partition Coefficient in Mineral / Melt Systems
Partitioning of REEs in mineral/melt systems is governed
by several factors, namely, (i) Composition (Watson,
1976; Ryerson and Hess, 1978); (ii) Temperature (Dunn,
1987; Leemand and Lindstorm, 1978); (iii) Pressure
(Green and Pearson, 1983, 1986); (iv) Oxygen fugacity
(Drake and Weill, 1975);(v) Crystal chemistry (Onuma et
al., 1968; Matsui et al., 1977; Phillpotts et al., 1978); (vi)
Water content of melt (Green and Pearson, 1986); and
(vii) Selection of proper partition coefficient (Rollinson,
1993). Figure 1 compares the partition coefficient versus
atomic number of REEs in common minerals in basaltic,
andesitic and rhyolitic melts (data from Rollinson, 1993
and references therein).
BEHAVIOUR OF RARE EARTH ELEMENTS IN
ROCKS AND SEDIMENTS
Behaviour of Rare Earth Elements in Igneous Rocks
In Igneous rocks, REE have preferential accumulation in
early forming ultrabasic and basic rocks as compared to
late forming intermediate and acidic rocks. Among the
basic and ultrabasic igneous rocks, alkali-rich basalts,
 Kirtikumar Randive and Others
ijolites and kimberlites have very high LREE contents
and (La/Lu)cn ratios, consistent with their formation by
small degree of melting of garnet peridotite. The lower
REE contents and La/Lu ratios in the tholeiites compared
to alkali basalts could be due to higher degrees of partial
melting required to produce tholeiites as compared to
alkali basalts (Henderson, 1984).
The ultramafic rocks and kimberlite clan rocks are
characterized by their large absolute REE abundance
(REE= 115-4613 ppm), large LREE/HREE ratios
((La/Lu)cn = 15.8-216) and the linear REE patterns,
with or without Eu anomalies in chondrite-normalized
plots (Burkov and Podporina, 1966; Heskin et al., 1966;
Philpotts et al., 1972; Reitz and Cullers, 1980; Cullers et
al., 1982)
Among the magmatic rocks, carbonatites
are known to possess the largest REE contents
(REE= 72-15,515 ppm) and LREE/HREE ratios
((La/Lu)cn = 7.1-1240) on earth (Vainshtein et al., 1961;
Kapustin, 1966; Barber, 1974; Cullers and Medaris,
1977; Armbrustmacher, 1979). Carbonatites have no
Eu anomalies, but some have negative Ce anomalies.
Samples with no Ce anomalies may have formed under
less oxidizing conditions than those with Ce anomalies.
Lamprophyres have similar REE contents (REE= 261-
1033 ppm) and large LREE/HREE ratios (La/Lu)cn = 20-
55 like Kimberlites. However, alkaline and ultramafic
varieties show REE patterns closer to carbonatites than
kimberlites. In contrast, komatites contain fairly low
REE contents (REE= 10.1-59.1 ppm) and LREE/
HREE ratios (La/Lu)cn = 0.24-4. Within a given komatiite
suite REE contents and (La/Lu)cn ratios increases with
decreasing MgO (Herrmann et al., 1976; Arth et al.,
1977; Echeverria, 1980; Jahn et al., 1980; Henderson,
1984).
Nevertheless, there is considerable overlap in the
REE content of group of ultrabasic and basic rocks. In
summary the decreasing abundance of REE contents of
magmatic rocks show following order: Carbonatites>
ultramfic and alkaline lamprophyres, ijolite and
associated alkali rocks > kimberlite clan rocks and calc-
alkaline lamprophyres > alkali Basalts > continental
tholeiites> komatiites. There is a tendency for the LREE/
HREE ratio or (La/Lu)cn ratio to decrease with decreasing
REE contents. Most basic and ultrabasic rocks do not
contain Eu anomalies, in marked contrast, to more silicic
rocks (Henderson, 1984).
The silicic rocks, especially andesites and granitic
rocks can be derived from different source materials and
by a variety of crystallization paths. This makes it even
more difficult to limit possible hypotheses for the origin
of these rock types when compared to basic and ultrabasic
rocks. In addition, small amounts of accessory minerals
that concentrate the REE, may control the REE contents
during melting or crystallization (Rollinson, 1993).
Andesites contain low to moderate REE contents
(REE= 25-341 ppm) and LREE/HREE ratios
(La/Lu)cn = 1.0- 21.5; they seldom have Eu anomalies and
only minor if present (Taylor, 1968, 1969; Condie and
Baragar, 1974). As summarized in a review of andesite
petrogenesis by Gill (1978), REE contents increases
with increasing K for a given Si in andesite suites. The
REE contents correlate well with the increasing vertical
distance from the subduction zone. Within a given suite
REE content increases with increasing silica (Henderson,
1984).
For anorthosites the REE contents (REE= 1.7-
148 ppm) and LREE/HREE ratios (La/Lu)cn = 0.13-58
are fairly low and most anorthosites contain positive Eu
anomalies (Philpotts et al., 1966; Anderson and Cullers,
1978; Ashwal and seifert, 1980). Plagioclase separates
in anorthosites contain lower REE concentrations
(REE= 0.7-57.6 ppm), larger LREE/HREE ratios
(La/Lu)cn = 0.84- 37 and larger positive Eu anomalies
than the anorthosite from which the plagioclase has
been removed. This is because the mafic minerals in
the anorthosite contain large REE contents, smaller
LREE/HREE ratios and smaller Eu anomalies than
the coexisting plagioclase. The positive Eu anomaly
generally shown by anorthosites suggests that they are
cumulates. The trondhjemites, tonalities, quartz diorites
and granodiorites that have positive Eu anomalies have
low absolute REE contents (REE= 10.5-144 ppm)
more similar to island arc abundances, but they have
fairly large LREE/HREE ratios ((La/Lu)cn =5.0-77.5).
Similarly, monzogranites and syenogranites have low to
moderate REE Content (REE= 8-1977 ppm) and low
to moderate LREE/HREE ratios ((La/Lu)cn =0.54- 137).
However, positive Eu anomalies are less common in
monzogranities and syenogranites than in granodiorite,
quartz diorites, tonalite or trondhjemites (Henderson,
1984).
Behaviour of Rare Earth Elements in Sedimentary
Rocks
One may expect that geochemical behavior of elements,
especially REE, may not yield coherent results, mostly
because REEs are not easily fractionated during
sedimentation; although the residual concentration
processes leading to formation of laterites and bauxites
exhibit reasonable control over REE distribution (e.g.
Meshram and Randive, 2011). However, a remarkable
uniformity is observed in the REE patterns of
sedimentary rocks in spite of considerable diversity at
their source. Such behavior leads us to conclude that the
sedimentary processes provide an efficient sampling of
the REE in the exposed crust. Several field based studies
have suggested REE mobility during weathering but
there is little agreement regarding the overall magnitude
or the potential for fractionation among them (e.g.,
Ronov et al., 1967; Nesbitt, 1979; Duddy, 1980; Topp
et al., 1984; Cullers et al., 1987; Middelburg et al.,
1988). The REEs are mobilized during weathering but
are primarily recycled within the weathering profile
rather than transported significant distances in solution
(Nesbitt, 1979). Thus for the most common weathering
 Understanding the Behaviour of Rare Earth Elements
condition, REE are dominantly transported from the
weathering profile by Mechanical processes (Nesbitt,
1979; Middleburg et al., 1988).
Three major factors associated with sedimentary
sorting may affect REE pattern in sediments: grain
size contrast, general mineralogy and heavy mineral
fractionation. REE abundance in various grain sizes
have been examined by cullers et al. (1979). They
found that the bulk of REE reside in the silt and clay
size fraction, although there is no direct correlation with
clay mineralogy, perhaps suggesting that trivalent REE
may be readily accommodated in most clay minerals.
Silt fractions tend to have lower overall abundances in
comparison to clay fractions although the shape of the
REE pattern is similar, suggesting the major control is a
dilution effect from quartz, a mineral with very low REE
abundances.
Other minerals like calcite and dolomite also have
fairly low REE abundances (although commonly higher
than that of quartz). If carbonate minerals (or other
minerals) are precipitated in equilibrium with sea water,
they typically possess negative Ce-anomalies which may
also be reflected in the bulk REE pattern (e.g., Piper,
1974; Palmer, 1985). On the other hand, clay minerals
have much higher total REEs; therefore the concentration
of clay minerals in mud and clays result in high REE
abundances.
The heavy minerals such as sphene, zircon,
allanite, monazite are usually enriched in REEs. Many of
these minerals may be concentrated during sedimentary
sorting processes; their presence may strongly influence
the overall patterns of REEs in the given rock
Behaviour of Rare Earth Elements in Metamorphic
Rocks
The REE content of metamorphic rocks is assumed to be
similar to that of their protolith; however, it is observed
that under some circumstances the REEs are mobile,
whereas, in other circumstances they are immobile. Thus
the overall REE abundance of metamorphic rocks may
differ considerably from their protoliths.
The residence of REEs in metamorphic rocks
depends on the minerals present in that rock. Therefore,
the modal abundance of those minerals and the physical
and chemical conditions in which those minerals grew
(assuming that the minerals were not subsequently
altered) pose strong constraint on REEs distribution in
metamorphic rocks. The changes in mineral assemblages
and mineral composition have been extensively
documented for a wide variety of metamorphic terranes
and are summarized in numerous textbooks and papers
(e.g. Winkler, 1976; Miyashiro, 1973; Ferry, 1982).
It is observed that the accessory minerals (zircon,
monazite, xenotime, allanite, sphene, apatite) tend to
concentrated REE much more than do the major rock
forming minerals such as feldspars, micas, pyroxenes and
amphiboles. Quartz has a very low REE content. The REE
concentration of individual minerals and partitioning
of REEs between minerals are controlled by the P-T-X
condition in which the minerals form and a variety of
crystallo-chemical factors, such as valence and effective
ionic radius (Adams, 1968; Fleischer, 1965; Fleischer
and Alteschuler, 1969; Jensen, 1973; Khomyakov, 1967;
Reitan et al., 1980; Henderson, 1984).
Petrologic data describing the reactions (both
continuous and discontinuous) that occurred during
metamorphism should be especially useful in determining
reasonable constraints. For example, if garnets were
to be disappear, the REE (especially HREE) released
would have to leave the system or to be incorporated in
other phases. Such reactions should be studied in detail
to estimate overall influence of metamorphism on REE
distribution.
Behaviour of Rare Earth Elements in Palaeogene
Neogene Holocene Systems
We do not have an exclusive estimate of either
abundance or enrichment-depletion of REEs in the
Palaeogene-Neogene systems, although we may look
into geochemical affinities and source inheritance of
magmas through the geological past. However, REEs
have been increasingly applied in the study of Palaogene
Neogene Holocene systems. Variety of media
e.g. extruded magmas, pyroclastic products (mainly
volcanic ash), wind-borne sediments and alluvial soils,
were effectively used to study these rocks. We have
selected examples from Palaeogene Neogene systems,
where REEs have been used to investigate diversity of
geological problems; a summary which is presented in
Table 2. The data allows drawing few generalizations:
Large number of media could be used to investigate
absolute and relative abundance of REEs; most common
being the volcanic rocks and their products and sediments
(both semi-consolidated as well as unconsolidated).
REE isotopes (e.g. 144Sm/143Nd) can provide
important information on the mantle source regions from
where these magmas have been generated.
The REE carrier minerals could have been
transported, incorporated or recycled during various
stages of evolution, which make them less useful for
petrogenetic interpretations. However, they find particular
importance in the study of carbonatite magmatism of
Palaeogene Neogene Holocene ages (see Le Bas et
al., 1987; Stoppa et al., 2009; Tucker et al., 2012).
Volcanic ash erupted from acid volcanoes, such
as Krakatau and Toba in Indonesia, travels thousands of
kilometers and deposited in far-flung areas such as India,
Myanmar, Bangladesh, etc. Source inheritance of such
materials could be studied using REEs (e.g. Pattan et al.,
2002).
REE geochemistry of the unconsolidated glacial
sediments or the windborne loess sediments can be
useful to decipher their source characteristics (Srivastava
et al., 2013; Sun et al., 2007).
Different sedimentary facies could be distinctly
studied using REE geochemistry (Rosetti et al., 2013)
 Kirtikumar Randive and Others

Table 2: Possible sources of information of rocks, minerals and sediments of Quaternary Period using rare earth elements.

Sr. Locality Media; Source material; Behavior of REEs Information reveled Reference
No. Geological Occurrence
1. Carrizozo, New Volcanic rocks; Mafic Chondrite normalized REE Geochemistry of the lavas shows Anthony et al.
Mexico igneous rocks; Cinder Cones patterns show strong partitioning transitional affinity between (1998)
and mafic Lava flows of REEs such as: LREE-enriched, hypersthene and nepheline normative
MREE-moderately enriched and basalts, which is similar to other
HREE-depleted patterns; typical of lavas in the region. The Radiogenic
alkaline/alkali-rich magmas. isotopes (including Sm-Nd) and
indicate that the magmas were
derived from a mantle source
enriched in incompatible elements
than the average asthenosphere, and/
or modified by crustal contamination.
2. Okinawa Siliciclastic sediments; The UCC normalized REE patterns Discrimination plots based on REE Dou et al.
Trough, East Clayey silt, tephra; Core of Core sediments show fractionation parameters suggest that (2010)
China Sea samples of sediments significant fractionations of the the cored sediments have variable
middle REE (specially Gd and Eu), provenances over the last 30 ka. The
shown by higher values of (Gd/Yb) changing provenances of terrigenous
UCC relative to (La/Yb)UCC and sediments into the middle Okinawa
(La/Sm)UCC . Trough are closely related to the
evolution of oceanic circulation and
sea level in the East China Sea.
3. Hokkaido, North Volcanic rocks; basalt - The three groups of calc-alkaline Andesite of the calc-alkali series is Katsui et al.
Japan andesite - dacite - rhyolite magmas were distinguished in the abundant in the Quaternary (1978)
Suite; Stratovolcanoes, chondrite-normalized REE pattern. volcanic fields of Hokkaido, with
lava domes and pyroclastic The distribution patterns vary substantial amounts of basaltic
cones. similar to the ocean ridge tholeiite, rocks. Non-enrichment of Fe together
showing a tendency toward with Sc and Y, and the negative Eu
depletion or equality of LREE over anomaly frequently found in REE
HREE, whereas other two groups pattern, are characteristic features of
have a marked enrichment LREE the calc-alkalic rocks. These features
over HREE suggesting a common can be interpreted by fractional
source for them. A negative Eu crystallization of the same magma
anomaly is a characteristic feature under specific conditions; or fractional
of the calc-alkali rocks. melting of the same parental material.
4. Eastern Sierras Sediments; stacked fining- Palaeogene-Neogene and recent Granitic rocks show lower REE Piovano et al.
Pampeanas, upward cycles composed sediments have REE normalized concentrations than metamorphic (1998)
Argentina of fine gravel or sand at the patterns which are similar to rocks, consequently REE normalized
base and mud at the top; other REE patterns observed in and multi-elemental diagrams reveal
sediments of different facies terrigenous sedimentary rocks. The patterns that can be used in linking
such as alluvial fans, eolian alluvial and the eolian sediments sediments to their probable source
and braided fluivial deposits. show similar REE pattern shapes rocks. Positive correlations between
that can be related to the pattern of silt percentages and REE, or the
the modern-day samples. concentrations of Ce, Nd, Eu and Tb,
indicate an enrichment of all these
elements in the silt-size fraction.
5. Marajo Island, Sediments core samples; The sediments formed in fluvial- Multivariate analysis of trace and rare Rossetti et
Northern Brazil six facies associations influenced environments display earth elements allowed distinguishing al. (2013)
including: fluvial channel, higher REE, higher LREE with five geochemical groups in agreement
outer estuary, central consequent lower HREE than with previous interpretations of
estuarine basin, tidal flat, marine-influenced deposits. The depositional environments consisting
estuarine channel, and sediments derived from tidal of fluvial, outer estuary, central
lagoon; estuarine deposits. flat and central estuarine basin estuarine basin, tidal flat, and lagoon.
displayed the lowest concentration Statistical analyses allowed a clear
in REE and LREE and the distinction between fluvial-influenced
highest concentration in HREE. and marine-influenced deposits.
 Understanding the Behaviour of Rare Earth Elements

6. Southern Tibet Loess sediments; loess
covered river terraces,
foothills of mountains, loess
mantle blanketing mountain
hills; loess dunes
7. Red Sea area, Quaternary alkaline volcanic
NE Africa rocks; basalts, alkali basalts,
and Arabian vesicular and porphyritic
Peninsula basalts; volcanic cones and
lava flows
8. Chukchi Sea in Marine sediments; coarse
the south of the and fine-grained surface
Arctic Ocean sediments; epicontinental
sea in the Arctic circle.
9. Schirmacher Unconsolidated sediments
Oasis, East from the four glaciological
Antarctica environments, namely,
polar ice sheet, inland lake,
channels, shelf region; loose
sediments.
Tibetan loess has higher values of
LREE/HREE and Ce/Yb than the
samples from the Loess Plateau.
Both the LREE/HREE vs Eu/Eu*
and the Ce/Yb vs Eu/Yb plots show
geographic distinctions, implying
their source areas are different.
Moreover, samples from the Loess
Plateau show less compositional
variability.
The analysed Sr-Nd-Pb isotope
ratios and REE compositions of
basaltic rocks from an 800 km long
profile along the Gulf of Aden
indicates three mantle source end-
members with N-type MORB,
HIMU-type and hybrid EM1-EM2
characteristics.
The sediments in the east and the
south of the Chukchi Sea have low
REE concentrations and evident
negative Ce anomalies and the
positive Eu anomaly in the coarse-
grained sediments.
The REE pattern is smooth,
showing both curves are mirror
images, in which the finer fraction
is more depleted compared to the
coarse fraction. The curves LREE
depleted show a negative Eu
anomaly and flat HREE.
Geochemical, mineralogical, and Sun et al.
granulometric evidence indicates that (2007)
the source materials of the Tibetan
loess are quite different from eolian
deposits on the Loess Plateau. loess
in southern Tibet has a glacial
origin, resulting from eolian sorting of
glaciofluvial outwash deposits from
braided river channels or alluvial fans
by local near-surface winds.
The relative contributions to the Volker et al.
magmas as a function of space and (1997)
time have been evaluated. The,
detailed studies of basaltic rocks
has led to a better understanding of
dynamic mantle processes related
to lithospheric extension, seafloor
spreading and plume interaction.
REEs tend to be enriched in fine- Zhihua et al.
grained sediments and deplete in (2003)
coarse-grained sediments. Most of
samples have flat shale-normalized
REE pattern in the Chukchi Sea,
indicating that surface sediments
are composed mainly of terrigenous
components derived from the
surrounding landmasses and have
experienced only weak chemical
weathering.
The behavior of REEs has indicated Srivastava
relative impoverishment of the REE et al. (2013)
carrier minerals such as garnet,
epidote and other mafic minerals
in the finer fraction. Poor sorting
of the glacial sediments and
absence of carbonates, apatite and
impoverishment in plagioclase may
also be among the reasons.

SUMMARY decreasing abundance of REEs. Among the sedimentary

Rare earth elements are reliable petrogenetic
indicators; they have unique properties such as strong
electropositive character, constancy in valance state (3+)
with exception of Eu and Yb showing additional (2+) and
Ce and Tb showing additional (4+) valence, significant
substitution especially of tetravalent cations in different
minerals, and their systematic partitioning in the mineral/
melt systems.
REEs (especially LREEs) are among the most
incompatible elements and therefore enrich the magmas
having low degrees of partial melting and metasomatised
source rocks. Carbonatites readily qualify these
conditions and therefore be the major reservoirs of REEs
in the crustal rocks. Following the suit, ultramafic and
alkaline lamprophyres, alkaline rocks such as ijolite,
kimberlite clan rocks, peridotites and komatiites have
processes, weathering is effective transporter of REEs.
Clay minerals were observed to retain majority of REEs
in the sediments. The remarkable uniformity in the REE
patterns in sedimentary rocks makes them important
geochemical indicators of sedimentary processes.
Behavior of REEs in metamorphic rocks depends on
their protolith and P-T-X conditions; accessory minerals
such as garnet, zircon, monazite, xenotime, allanite,
sphene, apatite, quartz, and others, greatly influence REE
distribution among metamorphic rocks.
Behavior of REEs in Palaeogene-Neogene-
Holocene Systems needs to be studied in details. It has
been demonstrated here that proper sampling of media
such as bed rock, unconsolidated and consolidated
sediments, loess and most importantly volcanic ash,
could effectively be used to study these systems using
REE geochemistry.
 Kirtikumar Randive and Others
ACKNOWLEDGEMENTS
We thank Guest Editors for inviting us to contribute
a paper for this special issue of the Gondwana Geological
Magazine. Facilities created during implementation
of Department of Science and Technology (DST)
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