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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 properties. The major difference between REE is their


size, which decreases with increasing atomic number.
Rare earth elements or lanthanides comprised a
series of elements between La (57) and Lu (71), show
This variation is due to the increased nuclear charge,
remarkable similarity in their oxidation states (3+) and which is only partially shielded by the 4f electrons; this
chemical properties. The trivalent REEs show significant feature is also known as lanthanide contraction. Due
substitution for Mn2+, Ca2+, Y3+, Th4+ and Zr4+; which greatly to size differences, REE can preferentially substitute in
influences their partitioning in various mineral phases, different minerals. Though such difference is small, it has
such as plagioclase, allanite, apaptite, monazite and zircon. a significant bearing on partitioning of REEs in different
The partitioning of REEs in mineral/melt systems had minerals (Henderson, 1984; Boynton, 1989; Rollinson,
been thoroughly investigated, and as such their partition 1993; Randive, 2012).
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, GENERAL CHARACTERISTICS OF
fractionation, heterogeneity, assimilation or contamination RARE EARTH ELEMENTS
and metasomatism. On the other hand, REEs do not
fractionate readily during sedimentation, nevertheless, a Oxidation States
remarkable uniformity is observed in the REE patterns
of sedimentary rocks. Weathering processes are however, The REEs which are strongly electropositive, prefer ionic
known to fractionate REEs. In case of metamorphic rocks, over covalent bonding and during ionization, first electrons
the protolith composition and P-T-X conditions influence to be removed are two from 6S, followed by 5d and 4f
distribution and mobility of REEs. Behavior of REEs sub-shells. All REEs show remarkably constant valence of
in Palaeogene-Neogene-Holocene systems depends on three. However, Eu and Yb can exist in 2+; whereas Ce and
the media being samples, e.g. volcanic rocks, pyroclastic Tb in 4+ oxidation states (Hendersen, 1984).
products mostly volcanic ash, wind-borne sediments and
alluvial soils. With the proper understanding of the system Oxygen Fugacity
being investigated, REEs may prove to be useful tracer of a
wide range of petrogenetic processes. The Eu2+/Eu3+ ratio is a good indicator of oxygen
fugacity prevailing during formation of minerals (Towell
Keywords: : REE, Minerals, Rocks et al., 1965; Phillpotts, 1970; Drake, 1975). The close
similarity in the ionic radii and charge of Sr2+ and Eu2+
INTRODUCTION would lead to almost identical partitioning behavior of
the two ions in the rock systems. This similarity could
The Rare Earth Elements (REE), commonly be used to calculate the Eu2+/Eu3+ ratio, and hence the
known as lanthanides, having atomic numbers ranging oxygen fugacity in a system where the partitioning of
from Lanthanum (La) 57 to Lutetium (Lu) 71. However, Eu2+ is significantly different from Eu3+ (Phillpotts, 1970).
Scandium (Sc) and Yttrium (Y) are also included in For e.g. when two phases (Phase I and Phase II) are in
the series. But Scandium which does not behave like equilibrium, their europium concentration relationship
REE is not preferred in the series by geochemists. The can be explained by following equations:
lanthanides have very similar geochemical properties [Eu]Phase I = [Eu2+]Phase I + [Eu3+]Phase I
because they occur in 3+ ionic forms in nature. However,
Europium (Eu) also occur in 2+ (larger ion) and [Eu]Phase II = [Eu2+]Phase II + [Eu3+]Phase II
Cerium (Ce) in 4+ (smaller ion) oxidation states. They Thus,
only differ in number of electrons in the 4f shell; this
[Eu]Phase II = D2+Phase II/Phase I ([Eu]Phase I [Eu3+]Phase I) +
shell has no involvement in forming chemical bonds,
therefore the elements have very similar chemical 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
occupy six-fold coordination sites, but the REE minerals
(D3+Phase II/Phase I D2+Phase II/Phase I)
rarely show this coordination. On the contrary, they tend
Also,
to show greater coordination, such as seven-fold (sphene),
[Eu2+]Phase I = [Eu]Phase I [Eu3+]Phase I eight-fold (zircon), nine-fold (monazite), eleven-fold
Where, Dn+Phase II/Phase I is the distribution coefficient value (allanite), and twelve-fold (perovskite).
for Sr between Phase II and Phase I.
Ionic Radius
This method has been applied successfully to
europium distribution amongst feldspar, pyroxene and Comparison of the relative sizes of the REE ions with
matrix phases of basalts, andesites and dacites (Phillpotts, those of other cations shows that there are few ions of
1970; Hendersen, 1984). similar sizes. Na+ and Ca2+ have similar sizes (six-fold
coordination). Eu2+ has similar radius to that of Sr2+ (See
Element Coordination
Table 1). K+, Rb+, Cs+ and Ba2+ are larger than trivalent
The REEs occupy a wide variety of coordination polyhedron 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 175

smaller, with the exception of Mn2+, Y3+, Th4+ and U4+ coordination polyhedron (e.g. allanite) favor larger
(Hendersen, 1984; Rollinson, 1993). ions (LREE), while those having relatively smaller
polyhedron (e.g. zircon) favor HREE.
Substitution in Minerals
Ionic substitution plays an important role in governing the Partition Coefficient in Mineral / Melt Systems
substitution of trace elements (Goldschimdt, 1937). The Partitioning of REEs in mineral/melt systems is governed
large ionic radii of REE preclude significant substitution by several factors, namely, (i) Composition (Watson,
of these elements into minerals. substitution of trivalent 1976; Ryerson and Hess, 1978); (ii) Temperature (Dunn,
REE are observed for Ca2+, Y3+, Th4+, U4+, Mn2+ and Zr4+. 1987; Leemand and Lindstorm, 1978); (iii) Pressure
Due to large variation in ionic radii of REEs different (Green and Pearson, 1983, 1986); (iv) Oxygen fugacity
minerals provide selective substitution for them. For (Drake and Weill, 1975);(v) Crystal chemistry (Onuma et
e.g. apatite prefers LREEs whereas garnet preferentially al., 1968; Matsui et al., 1977; Phillpotts et al., 1978); (vi)
substitutes HREEs in their crystal structures. Common Water content of melt (Green and Pearson, 1986); and
exchange reactions for substitution include following: (vii) Selection of proper partition coefficient (Rollinson,
R3+ + Al3+ + CaAl2Si2O8 RAl3SiO8 + Ca2++Si4+ 1993). Figure 1 compares the partition coefficient versus
R3+ + Na+ + 2CaAl2Si2O8 2C (R, Na) Al2Si2O8 + 2Ca2+ atomic number of REEs in common minerals in basaltic,
andesitic and rhyolitic melts (data from Rollinson, 1993
2R3+ + Ca5(PO4)3OH (R2 Ca2) (PO4)3OH + 3Ca2+ and references therein).
(Where symbol stands for Vacancy)
Partition BEHAVIOUR OF RARE EARTH ELEMENTS IN
Onuma et al. (1968) and Jensen (1973) demonstrated
ROCKS AND SEDIMENTS
the influence of ionic radius and ionic charge on the
Behaviour of Rare Earth Elements in Igneous Rocks
patitioning of elements in mineral/melt systems.
They plotted logD against ionic radius diagrams and In Igneous rocks, REE have preferential accumulation in
demonstrated that the ions having same charge show early forming ultrabasic and basic rocks as compared to
fairly smooth curve, which is due to presence of Eu2+ late forming intermediate and acidic rocks. Among the
along with Eu3+. Therefore, these minerals having larger basic and ultrabasic igneous rocks, alkali-rich basalts,

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).
Kirtikumar Randive and Others

ijolites and kimberlites have very high LREE contents only minor if present (Taylor, 1968, 1969; Condie and
and (La/Lu)cn ratios, consistent with their formation by Baragar, 1974). As summarized in a review of andesite
small degree of melting of garnet peridotite. The lower petrogenesis by Gill (1978), REE contents increases
REE contents and La/Lu ratios in the tholeiites compared with increasing K for a given Si in andesite suites. The
to alkali basalts could be due to higher degrees of partial REE contents correlate well with the increasing vertical
melting required to produce tholeiites as compared to distance from the subduction zone. Within a given suite
alkali basalts (Henderson, 1984). REE content increases with increasing silica (Henderson,
The ultramafic rocks and kimberlite clan rocks are 1984).
characterized by their large absolute REE abundance For anorthosites the REE contents (REE= 1.7-
(REE= 115-4613 ppm), large LREE/HREE ratios 148 ppm) and LREE/HREE ratios (La/Lu)cn = 0.13-58
((La/Lu)cn = 15.8-216) and the linear REE patterns, are fairly low and most anorthosites contain positive Eu
with or without Eu anomalies in chondrite-normalized anomalies (Philpotts et al., 1966; Anderson and Cullers,
plots (Burkov and Podporina, 1966; Heskin et al., 1966; 1978; Ashwal and seifert, 1980). Plagioclase separates
Philpotts et al., 1972; Reitz and Cullers, 1980; Cullers et in anorthosites contain lower REE concentrations
al., 1982) (REE= 0.7-57.6 ppm), larger LREE/HREE ratios
Among the magmatic rocks, carbonatites (La/Lu)cn = 0.84- 37 and larger positive Eu anomalies
are known to possess the largest REE contents than the anorthosite from which the plagioclase has
(REE= 72-15,515 ppm) and LREE/HREE ratios been removed. This is because the mafic minerals in
((La/Lu)cn = 7.1-1240) on earth (Vainshtein et al., 1961; the anorthosite contain large REE contents, smaller
Kapustin, 1966; Barber, 1974; Cullers and Medaris, LREE/HREE ratios and smaller Eu anomalies than
1977; Armbrustmacher, 1979). Carbonatites have no the coexisting plagioclase. The positive Eu anomaly
Eu anomalies, but some have negative Ce anomalies. generally shown by anorthosites suggests that they are
Samples with no Ce anomalies may have formed under cumulates. The trondhjemites, tonalities, quartz diorites
less oxidizing conditions than those with Ce anomalies. and granodiorites that have positive Eu anomalies have
Lamprophyres have similar REE contents (REE= 261- low absolute REE contents (REE= 10.5-144 ppm)
1033 ppm) and large LREE/HREE ratios (La/Lu)cn = 20- more similar to island arc abundances, but they have
55 like Kimberlites. However, alkaline and ultramafic fairly large LREE/HREE ratios ((La/Lu)cn =5.0-77.5).
varieties show REE patterns closer to carbonatites than Similarly, monzogranites and syenogranites have low to
kimberlites. In contrast, komatites contain fairly low moderate REE Content (REE= 8-1977 ppm) and low
REE contents (REE= 10.1-59.1 ppm) and LREE/ to moderate LREE/HREE ratios ((La/Lu)cn =0.54- 137).
HREE ratios (La/Lu)cn = 0.24-4. Within a given komatiite However, positive Eu anomalies are less common in
suite REE contents and (La/Lu)cn ratios increases with monzogranities and syenogranites than in granodiorite,
decreasing MgO (Herrmann et al., 1976; Arth et al., quartz diorites, tonalite or trondhjemites (Henderson,
1977; Echeverria, 1980; Jahn et al., 1980; Henderson, 1984).
1984).
Behaviour of Rare Earth Elements in Sedimentary
Nevertheless, there is considerable overlap in the
Rocks
REE content of group of ultrabasic and basic rocks. In
summary the decreasing abundance of REE contents of One may expect that geochemical behavior of elements,
magmatic rocks show following order: Carbonatites> especially REE, may not yield coherent results, mostly
ultramfic and alkaline lamprophyres, ijolite and because REEs are not easily fractionated during
associated alkali rocks > kimberlite clan rocks and calc- sedimentation; although the residual concentration
alkaline lamprophyres > alkali Basalts > continental processes leading to formation of laterites and bauxites
tholeiites> komatiites. There is a tendency for the LREE/ exhibit reasonable control over REE distribution (e.g.
HREE ratio or (La/Lu)cn ratio to decrease with decreasing Meshram and Randive, 2011). However, a remarkable
REE contents. Most basic and ultrabasic rocks do not uniformity is observed in the REE patterns of
contain Eu anomalies, in marked contrast, to more silicic sedimentary rocks in spite of considerable diversity at
rocks (Henderson, 1984). their source. Such behavior leads us to conclude that the
The silicic rocks, especially andesites and granitic sedimentary processes provide an efficient sampling of
rocks can be derived from different source materials and the REE in the exposed crust. Several field based studies
by a variety of crystallization paths. This makes it even have suggested REE mobility during weathering but
more difficult to limit possible hypotheses for the origin there is little agreement regarding the overall magnitude
of these rock types when compared to basic and ultrabasic or the potential for fractionation among them (e.g.,
rocks. In addition, small amounts of accessory minerals Ronov et al., 1967; Nesbitt, 1979; Duddy, 1980; Topp
that concentrate the REE, may control the REE contents et al., 1984; Cullers et al., 1987; Middelburg et al.,
during melting or crystallization (Rollinson, 1993). 1988). The REEs are mobilized during weathering but
Andesites contain low to moderate REE contents are primarily recycled within the weathering profile
(REE= 25-341 ppm) and LREE/HREE ratios rather than transported significant distances in solution
(La/Lu)cn = 1.0- 21.5; they seldom have Eu anomalies and (Nesbitt, 1979). Thus for the most common weathering
Understanding the Behaviour of Rare Earth Elements

condition, REE are dominantly transported from the of REEs between minerals are controlled by the P-T-X
weathering profile by Mechanical processes (Nesbitt, condition in which the minerals form and a variety of
1979; Middleburg et al., 1988). crystallo-chemical factors, such as valence and effective
Three major factors associated with sedimentary ionic radius (Adams, 1968; Fleischer, 1965; Fleischer
sorting may affect REE pattern in sediments: grain and Alteschuler, 1969; Jensen, 1973; Khomyakov, 1967;
size contrast, general mineralogy and heavy mineral Reitan et al., 1980; Henderson, 1984).
fractionation. REE abundance in various grain sizes Petrologic data describing the reactions (both
have been examined by cullers et al. (1979). They continuous and discontinuous) that occurred during
found that the bulk of REE reside in the silt and clay metamorphism should be especially useful in determining
size fraction, although there is no direct correlation with reasonable constraints. For example, if garnets were
clay mineralogy, perhaps suggesting that trivalent REE to be disappear, the REE (especially HREE) released
may be readily accommodated in most clay minerals. would have to leave the system or to be incorporated in
Silt fractions tend to have lower overall abundances in other phases. Such reactions should be studied in detail
comparison to clay fractions although the shape of the to estimate overall influence of metamorphism on REE
REE pattern is similar, suggesting the major control is a distribution.
dilution effect from quartz, a mineral with very low REE
Behaviour of Rare Earth Elements in Palaeogene
abundances.
Neogene Holocene Systems
Other minerals like calcite and dolomite also have
fairly low REE abundances (although commonly higher We do not have an exclusive estimate of either
than that of quartz). If carbonate minerals (or other abundance or enrichment-depletion of REEs in the
minerals) are precipitated in equilibrium with sea water, Palaeogene-Neogene systems, although we may look
they typically possess negative Ce-anomalies which may into geochemical affinities and source inheritance of
also be reflected in the bulk REE pattern (e.g., Piper, magmas through the geological past. However, REEs
1974; Palmer, 1985). On the other hand, clay minerals have been increasingly applied in the study of Palaogene
have much higher total REEs; therefore the concentration Neogene Holocene systems. Variety of media
of clay minerals in mud and clays result in high REE e.g. extruded magmas, pyroclastic products (mainly
abundances. volcanic ash), wind-borne sediments and alluvial soils,
The heavy minerals such as sphene, zircon, were effectively used to study these rocks. We have
allanite, monazite are usually enriched in REEs. Many of selected examples from Palaeogene Neogene systems,
these minerals may be concentrated during sedimentary where REEs have been used to investigate diversity of
sorting processes; their presence may strongly influence geological problems; a summary which is presented in
the overall patterns of REEs in the given rock Table 2. The data allows drawing few generalizations:
Large number of media could be used to investigate
Behaviour of Rare Earth Elements in Metamorphic
absolute and relative abundance of REEs; most common
Rocks
being the volcanic rocks and their products and sediments
The REE content of metamorphic rocks is assumed to be (both semi-consolidated as well as unconsolidated).
similar to that of their protolith; however, it is observed REE isotopes (e.g. 144Sm/143Nd) can provide
that under some circumstances the REEs are mobile, important information on the mantle source regions from
whereas, in other circumstances they are immobile. Thus where these magmas have been generated.
the overall REE abundance of metamorphic rocks may The REE carrier minerals could have been
differ considerably from their protoliths. transported, incorporated or recycled during various
The residence of REEs in metamorphic rocks stages of evolution, which make them less useful for
depends on the minerals present in that rock. Therefore, petrogenetic interpretations. However, they find particular
the modal abundance of those minerals and the physical importance in the study of carbonatite magmatism of
and chemical conditions in which those minerals grew Palaeogene Neogene Holocene ages (see Le Bas et
(assuming that the minerals were not subsequently al., 1987; Stoppa et al., 2009; Tucker et al., 2012).
altered) pose strong constraint on REEs distribution in Volcanic ash erupted from acid volcanoes, such
metamorphic rocks. The changes in mineral assemblages as Krakatau and Toba in Indonesia, travels thousands of
and mineral composition have been extensively kilometers and deposited in far-flung areas such as India,
documented for a wide variety of metamorphic terranes Myanmar, Bangladesh, etc. Source inheritance of such
and are summarized in numerous textbooks and papers materials could be studied using REEs (e.g. Pattan et al.,
(e.g. Winkler, 1976; Miyashiro, 1973; Ferry, 1982). 2002).
It is observed that the accessory minerals (zircon, REE geochemistry of the unconsolidated glacial
monazite, xenotime, allanite, sphene, apatite) tend to sediments or the windborne loess sediments can be
concentrated REE much more than do the major rock useful to decipher their source characteristics (Srivastava
forming minerals such as feldspars, micas, pyroxenes and et al., 2013; Sun et al., 2007).
amphiboles. Quartz has a very low REE content. The REE Different sedimentary facies could be distinctly
concentration of individual minerals and partitioning 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 Tibetan loess has higher values of Geochemical, mineralogical, and Sun et al.
covered river terraces, LREE/HREE and Ce/Yb than the granulometric evidence indicates that (2007)
foothills of mountains, loess samples from the Loess Plateau. the source materials of the Tibetan
mantle blanketing mountain Both the LREE/HREE vs Eu/Eu* loess are quite different from eolian
hills; loess dunes and the Ce/Yb vs Eu/Yb plots show deposits on the Loess Plateau. loess
geographic distinctions, implying in southern Tibet has a glacial
their source areas are different. origin, resulting from eolian sorting of
Moreover, samples from the Loess glaciofluvial outwash deposits from
Plateau show less compositional braided river channels or alluvial fans
variability. by local near-surface winds.
7. Red Sea area, Quaternary alkaline volcanic The analysed Sr-Nd-Pb isotope The relative contributions to the Volker et al.
NE Africa rocks; basalts, alkali basalts, ratios and REE compositions of magmas as a function of space and (1997)
and Arabian vesicular and porphyritic basaltic rocks from an 800 km long time have been evaluated. The,
Peninsula basalts; volcanic cones and profile along the Gulf of Aden detailed studies of basaltic rocks
lava flows indicates three mantle source end- has led to a better understanding of
members with N-type MORB, dynamic mantle processes related
HIMU-type and hybrid EM1-EM2 to lithospheric extension, seafloor
characteristics. spreading and plume interaction.
8. Chukchi Sea in Marine sediments; coarse The sediments in the east and the REEs tend to be enriched in fine- Zhihua et al.
the south of the and fine-grained surface south of the Chukchi Sea have low grained sediments and deplete in (2003)
Arctic Ocean sediments; epicontinental REE concentrations and evident coarse-grained sediments. Most of
sea in the Arctic circle. negative Ce anomalies and the samples have flat shale-normalized
positive Eu anomaly in the coarse- REE pattern in the Chukchi Sea,
grained sediments. indicating that surface sediments
are composed mainly of terrigenous
components derived from the
surrounding landmasses and have
experienced only weak chemical
weathering.
9. Schirmacher Unconsolidated sediments The REE pattern is smooth, The behavior of REEs has indicated Srivastava
Oasis, East from the four glaciological showing both curves are mirror relative impoverishment of the REE et al. (2013)
Antarctica environments, namely, images, in which the finer fraction carrier minerals such as garnet,
polar ice sheet, inland lake, is more depleted compared to the epidote and other mafic minerals
channels, shelf region; loose coarse fraction. The curves LREE in the finer fraction. Poor sorting
sediments. depleted show a negative Eu of the glacial sediments and
anomaly and flat HREE. absence of carbonates, apatite and
impoverishment in plagioclase may
also be among the reasons.

SUMMARY decreasing abundance of REEs. Among the sedimentary


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

ACKNOWLEDGEMENTS Research Project ESS/16/301/2006 and National Centre


for Antarctic and Ocean Research (NCAOR) Research
We thank Guest Editors for inviting us to contribute Project NCAOR/MoES/Nagpur University/2012 to KRR
a paper for this special issue of the Gondwana Geological is greatly appreciated. Dr. Sangodes persuasion made
Magazine. Facilities created during implementation KRR look in to the behavior of REEs in Palaeogene-
of Department of Science and Technology (DST) Neogene-Holocene Systems.

REFERENCES
Adams, J.W. (1968). Distribution of lanthanides in minerals. Acta, v.39, pp.55-64.
7th Rare Earth Res. Conf., San Diego, Calif., October, Drake, M.J. and Weill, D.F. (1975). Partition of Sr, Ba, Ca, Y,
1968, v.2, pp.639-650. Eu2+, Eu3+, and other REE between plagioclase feldspar
Anderson, J.L. and Cullers, R.L. (1978). Geochemistry and magmatic liquid: An experimental study. Geochim.
and evolution of the Wolf River batholiths, a Late Cosmochim. Acta, v.39, pp.689-712.
Precambrian rapakivi massif in north Wisconsin, U.S.A. Duddy, I.R. (1980). Redistribution and fractionation of rare
Precamb. Res., v.7, pp.287-324. earth and other elements in a weathering profile. Chem.
Armbrustmacher, T.J. (1979). Replacement and primary Geol., v.30, pp.363-381.
magmatic carbonatites from the Wet Mountains area, Dunn, T. (1987). Partitoning of Hf, Lu, Ti and Mn between
Fremont and Custer Counties, Colorado. Eco. Geol., olivine, clinopyroxene and basaltic liquid. Contrib.
v.74, pp.888-901. Mineral. Petrol., v.96, pp.476-484.
Arth, J.G., Arndt, N.T. and Naldrett, A.J. (1977). Genesis of Echeverria, L.M. (1980). Tertiary or Mesozoic komatiites
Archean komatiites from Munro Township, Ontario: from Gorgona Island, Columbia: field relations and
trace element evidence. Geology, v.5, pp.590-594. geochemistry. Contrib. Mineral. Petrol., v.73, pp.253-
Ashwal, L.D. and Seifert, K.E. (1980). Rare-earth-element 266.
geochemistry of anorthosite and related rocks from Ferry, J.M. (Ed.) (1982). Characterization of metamorphism
the Adirondocks, New York and other massif-type through mineral equilibria. Rev. Mineral., v.10, 397p.
complexes, Part I and II. Geol. Soc. America Bull., v.91, Fleischer, M. (1967). Some aspects of the geochemistry of
pp.105-107 (Part I), pp.659-684 (Part II) yttrium and the lanthanides. Geochim. Cosmochim.
Barber, C. (1974). The geochemistry of carbonatites and related Acta, v.29, pp.755-772.
rocks from two carbonatitecomplexs, south Nyonza, Fleischer, M. and Aultschuler, Z.S. (1969). The relationship
Kenya. Lithos.,v.7, pp.53-63. of the rare-earth composition of minerals to geologic
Boynton, W.V. (1989). Cosmochemistry of the rare earth environment. Geochim. Cosmochim. Acta, v.33, pp.725-
elements: condensation and evaporation processes. In: 732.
B.R. Lipin and G.A. McKay (Eds.), Geochemistry and Gill, J.B. (1978). Role of trace element partition coefficients
Mineralogy of Rare Earth Elements. Rev. Mineral., v.21, in models of andesite genesis. Geochim. Cosmochim.
pp.1-24. Acta, v.42, pp.709-724.
Burkov, V.V. and Podporina, Y.K. (1966). First data on rare Goldschmidt, V.M. (1937). The principle of distribution of
earth in kimberlites. Dokl. Akad. Nauk S.S.S.R., v.171, chemical elements in minerals and rocks. Jour. Chem.
pp.215-219. Soc., pp.655-672.
Condie, K.C. and Baragar, W.R.A. (1974). Rare-earth element Green, T.H. and Pearson, N.J. (1983). Effect of pressure on rare
distributions in volcanic rocks from Archean greenstone earth element partition coefficients in common magmas.
belts. Contrib. Mineral. Petrol., v.45, pp.237-246. Nature, v.305, pp.414-416.
Cullers, R.L. and Medaris, L.G. (1977). Rare earth elements in Green, T.H. and Pearson, N.J. (1986). Rare-earth element
carbonatite and cogenetic alkaline rocks: Examples from partitioning between sphene and coexisting liquid at
Seabrook Lake and Callander Bay, Ontario. Contrib. high pressure and temperature. Chem. Geol., v.55,
Mineral. Petrol., v.65, pp.143-153. pp.105-119.
Cullers, R.L., Chaudhari, S., Kilbane, N. and Koch, R. (1979). Henderson, P. (Ed.) (1984). Rare Earth Element Geochemistry.
Rare earth in size fractions and sedimentary rocks of Elsevier, Amsterdam, 510p.
Pennsylvanian-Permian age from the mid-continent of Herrmann, A.G., Blanchard, D.P., Haskin, L.A., Jacob, J.W.,
the U.S.A. Geochim. Cosmochim. Acta, v.43, pp.1285- Knake, D., Korotev, R.L. and Brannon, J.C. (1976).
1302. Major, minor and trace element compositions of
Cullers, R.L., Mullenax, J., Demarco, M. and Nordeng, S. peridotitic and basaltic komatites from the Precambrian
(1982). Trace element content and petrogenesis of crust of southern Africa. Contrib. Mineral. Petrol., v.59,
kimberlites, Riley County, Kansas. Am. Mineral., v.67, pp.1-12.
pp.223-233. Heskin, L.A., Frey, F.A., Schmitt, R.A. and Smith, R.H. (1966).
Cullers, R.L., Barrett, T., Carlson, R. and Robinson, B. Meteoritic, solar and terrestrial rare-earth distribution.
(1987). Rare earth element and mineralogic changes Phys. Chem. Earth., v.7, pp.167-321
in Holocene soil and stream sediments: a case study in Jahn, B., Auvray, B., Blais, S., Capdevila, R., Cornichet,
the wet mountains, Colorado, U.S.A. Chem. Geol., v.63, J., Videl, R. and Hameurt, J. (1980). Trace element
pp.275-297. geochemistry and petrogenesis of Finnish greenstone
Drake, M.J. (1975). The oxidation state of europium as an belts. Jour. Petrol., v.21, pp.201-244.
indicator of oxygen fugacity. Geochim. Cosmochim. Jensen, B.B. (1973). Patterns of trace element partitioning.
Understanding the Behaviour of Rare Earth Elements

Geochim. Cosmochim. Acta, v.37, pp.2227-2242 Riley County, Kansas. Geol. Soc. America Abstr. Prog.,
Kapustin, Y.L. (1966). Geochemistry of rare earth elements in v.12, pp.16 (abstract).
carbonatites. Geochem. Int., v.3, pp.1054-1064. Rollinson, H. (1993). Using geochemical data: evaluation,
Khomyakov, A.P. (1967). Chemical and crystallochemical presentation, interpretation. Longman Scientific &
factors in the distribution of rare earths. Geochem. Int., Technical, Essex, 352p.
v.4, pp.127-135. Ronov, A.B., Balashov, Yu.A. and Middisov, A.A. (1967).
Le Bas, M.J., Mian, I. and Rex, D.C. (1987). Age and nature of Geochemistry of the rare earths in the sedimentary
carbonatte emplacement in North Pakistan. Geol. Rund., cycle. Geochem. Int., v.4, pp.1-17.
v.76(2), pp.317-323. Rossetti, D.D.F., Munita, C.S. and Oliveira, P.M.S. (2012).
Leeman, W.P. and Lindstrom, D.J. (1978). Partitioning of Ni2+ Minor and rare earth element as a paleoenvironmental
between basaltic melt and synthetic melts and olivines markers of late quaternary sediments in Marajo Island,
an experimental study. Geochim. Cosmochim. Acta, Northern Brazil. Geochimica Brasiliensis, Ouro Preto.,
v.42, pp.801-816. v.26(1), pp.79-93.
Matsui, Y., Onuma, N., Nagasawa, H., Higuchi, H. and Banno, Srivastava, A.K., Randive, K.R. and Khare, N. (2013).
S. (1977). Crystal structure control in trace element Mineralogical and geochemical studies of glacial
partition between crystal and magma. Bull. Soc. Fr. sediments from Schirmacher Oasis, East Antarctica.
Mineral. Crystal., v.100, pp.315-324 Quater. Inter., v.292, pp.205-216.
Middleberg, J.J., van der Weijden, C.H. and Woittiez, J.R.W. Stoppa, F., Jones, A.P. and Sharygin, V.V. (2009). Nyerereite
(1988). Chemical processes affecting the mobility of fro carbonatite rocks at Vulture volcano: implications
major, minor and trace elements during weathering of for mantle metasomatism and petrogenesis of alkali
granitic rocks. Chem. Geol., v.68, pp.253-273. carbonate melts. Cent. Eur. Jour. Geosci., v.1(2), pp.131-
Miyashiro, A. (1973). Metamorphism and metamorphic belts. 151.
John Wiley & Sons, New York, 492p. Ryerson, F.J. and Hess, P.C. (1978). Implications of liquid-
Nesbitt, H.W. (1979). Mobility and fractionation of rare earth liquid distribution coefficients to mineral-liquid
elements during weathering of a granodiorite. Nature, partitioning. Geochim. Cosmochim. Acta, v.42, pp.921-
v.279, pp.206-210. 932.
Onuma, N., Higuchi, H., Wakita, H. and Nagasawa, H. (1968). Sun, J., Li, S.H., Muhs, D.R. and Li, B. (2007). Loess
Trace element partition between two pyroxenes and the sedimentation in Tibet: provenance, process, and link
host lava. Earth planet. Sci. Lett., v.5. pp.47-51. with Quaternary glaciations. Quater. Sci. Rev., v.26,
Palmer, M.R. (1985). Rare earth elements in foraminifera tests. pp.2265-2280.
Earth Planet. Sci. Lett., v.73. pp.285-298. Taylor, S.R. (1968). Geochemistry of andesites. In: L.H.
Pattan, J.N., Pearce, N.J.G. and Banakar, V.K. (2002). Origin Ahrens (Ed.), Origin and Distribution of the Elements,
of ash in Central Indian Ocean Basin and its implication pp.559-583, Pergamon, Oxford.
for the volume estimate of the 74,000 BP youngest Toba Taylor, S.R. (1969). Trace element chemistry of andesites and
eruption. Curr. Sci., v.83, pp.889-893. associated calc-alkaline rocks. In: Proceedings of the
Philpotts, J.A. (1978). A law of constant rejection. Geochim. Andesite Conference. Oreg., Dep. Geol. Miner. Ind.,
Cosmochim. Acta, v.42, pp.909-920. Bull., v.65, pp.43-63.
Philpotts, J.A., Schnetzler, C.C. and Thomas, H.H. (1966). Topp, S.E., Salbu, B., Roaldset, E. and Jorgensen, P. (1984).
Rare earth abundances in an anorthosite and a mangerite. Vertical distribution of trace elements in laterite soil
Nature, v.212, pp.805 (Suriname). Chem. Geol., v.47, pp.159-174.
Philpotts, J.A. and Schnetzler C.C. (1970). Phenocryst- Towell, D.G., Winchester, J.W. and Spirn, R.V. (1965). Rare
matrix partition coefficients for K, Rb, Sr and Ba with Earth Distributions in some rocks and associated
application to anorthosite and basalt genesis. Geochim. minerals of the batholiths of southern California. Jour.
Cosmochim. Acta, v.34, pp.307-322. Geophys. Res., v.70, pp.3485-3496.
Philpotts, J.A., Schnetzler, C.C. and Thomas, H.H. (1972). Tucker, R.D., Belkin, H.E., Schulz, K.J., Peters, S.G., Horton,
Petrogenetic implications of some new geochemical F., Buttleman, K., Scott, E.R. (2012). A major light
data on eclogitic and ultrabasic inclusions. Geochim. rare-earth element (LREE) resources in the Khanneshin
Cosmochim. Acta, v.36, pp.1131-1166. carbonatite complex, Southern Afghanistan. Econ.
Piper, D.Z. (1974). Rare earth elements in sedimentary cycle: a Geol., v.107, pp.197-208.
summary. Chem. Geol., v.14, pp.285-304. Vainshtein, E.E., Pozharitskaya, L.K. and Turanskaya, N.V.
Randive, K.R. (2012). Elements of Geochemistry, Geochemical (1961). Behavior of the rare earths in the process of
Exploration and Medical Geology. Research Publishing formation of carbonatites. Geochemistry (U.S.S.R.),
Services, Singapore, 457p. v.11, pp.1151-1154.
Reitan, P.H., Roelandts, I. and Brunfelt, A.O. (1980). Optimum Watson, E.B. (1976). Two liquid partition coefficients:
ionic size for substitution in the M (2) site in the experimental data and geochemical implications.
metamorphic diopside. N. Jahrb. Mineral. Monat., v.4, Contrib. Mineral. Petrol., v.56, pp.119-134.
pp.181-191. Winkler, H.G.F. (1976). Petrogenesis of metamorphic rocks.
Reitz, B. and Cullers, R.L. (1980). Petrogenesis of kimberlites, 4th edition, Springer, New York.

(Received : 17 December 2013; Revised form accepted : 5 February 2014)