International Scholarly Research Network

ISRN Soil Science

Volume 2012, Article ID 783876, 11 pages
doi:10.5402/2012/783876

Review Article
Rare Earth Elements: Their Importance in
Understanding Soil Genesis

Michael T. Aide and Christine Aide

Department of Agriculture, Southeast Missouri State University, 1 University Plaza, Cape Girardeau, MO 63701, USA

Correspondence should be addressed to Michael T. Aide, [email protected]

Received 5 January 2012; Accepted 23 February 2012

Academic Editors: G. Benckiser, L. Mercury, and W. Peijnenburg

Copyright © 2012 M. T. Aide and C. Aide. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.

The rare earth elements (REEs) are commonly defined as lanthanum (La) and the 14 elements comprising the Lanthanide series.
The REE’s typically exhibit trivalent oxidation states; however, Europium may also occur as Eu2+ and Cerium may occur as Ce4+ .
The REE’s ionic radii decrease on progression from La to Lu, which results in a slight but predictable change in their chemical
affinity. Typically, the light REE (La to Sm) reside in trace minerals such as apatite, epidote and allanite, whereas the heavy REE (Gd
to Lu) are associated with minerals such as zircon. Investigations typically show that the REE are depleted in near-surface horizons
and accumulate in deeper horizons or the regolith as clay-oxyhydroxide adsorbates or REE-phosphate precipitates. Numerous
studies show the heavy REE accumulating in the deeper soil regions to a greater extent than the light REE, whereas other studies
show the light REE’s preferentially accumulating at greater soil depths. The degree of interhorizon transport has great potential
to become an index of weather intensity. The various REE soil migration pathways have been isolated, including lessivage, soil
organic matter complexation, leaching in percolating water, adsorption by inorganic colloids, and precipitated by phosphate-
bearing minerals.

1. The Inorganic Chemistry of The uniqueness and importance of the REEs stem from
the Rare Earth Elements their chemical similarity attributed to the predominance
of trivalent REEs species forming an array of minerals
The rare earth elements (REEs) are commonly defined as lan- [1]. Although the lanthanide series is defined as elements
thanum (La) and the 14 elements comprising the Lantha- having partially to completely filled 4f-orbital ground-state
nide series: cerium (Ce), praseodymium (Pr), neodymium electronic configurations (Table 1), the Ln3+ species result
(Nd), promethium (Pm), samarium (Sm), europium (Eu), from having three electrons removed from their d, s, and f
gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium orbitals. The number of f orbital electrons remaining in each
(Ho), erbium (Er), thulium (Tm) ytterbium (Yb), and Ln3+ species corresponds with their order in the Lanthanide
lutetium (Lu). The Lanthanide series consists of unique ele- series (La has no f orbital electrons, Ce has one f orbital
ments characterized as having a ground state electronic con- electron, Pr has two f orbital electrons, to Lu having 14 f
figurations having at least one electron in the 4f electronic orbital electrons). The REEs display considerable ionic bond-
orbital. Yttrium (Y) is frequently included as a rare earth ing character and are considered hard acids, features attrib-
element because of its small ionic radius, approximately the uted to their s, d, and f orbital interactions [1].
same ionic radius as Ho. Lanthanum is frequently associ- Europium has a ground state electronic configuration
ated because of its position in the Periodic Table and its ([Xe] 4f7 6s2 ) with a half-filled f orbital, allowing particular
similar trivalent chemical affinity. The symbol Ln3+ is fre- stability for the Eu2+ species. The ionic radius of Eu2+ is very
quently used as a generic representation for the rare earth similar to that of strontium (Sr); therefore, Eu2+ participates
elements having trivalent cationic form. Promethium under- in isomorphic substitution with Sr2+ in selected minerals.
goes radioactive decay (half-life is 2.62 years) and its presence Similarly, Ce exhibits oxidation-reduction behavior and
in the natural environment is virtually nonexistent [1]. its electronic ground state configuration ([Xe] 4f1 5d1 6s2 )
2 ISRN Soil Science

Table 1: Chemical properties of the rare earth elements, including La, Sc, and Y.

Atomic1
Element
Number Weight Ground state Configuration1 Name
Trivalent REE
La 57 138.9055 [Xe]5d1 6s2 Lanthanum
Ce 58 140.12 [Xe]4f1 5d1 6s2 Cerium
Pr 59 140.9077 [Xe]4f3 6s2 Praseodymium
Nd 60 144.24 [Xe]4f4 6s2 Neodymium
Pm 61 145 [Xe]4f5 6s2 Promethium
Sm 62 150.36 [Xe]4f6 6s2 Samarium
Eu 63 151.96 [Xe]4f7 6s2 Europium
Gd 64 157.25 [Xe]4f7 5d1 6s2 Gadolinium
Tb 65 158.9254 [Xe]4f9 6s2 Terbium
Dy 66 162.50 [Xe]4f10 6s2 Dysprosium
Ho 67 164.9304 [Xe]4f11 6s2 Holmium
Er 68 167.26 [Xe]4f12 6s2 Erbium
Tm 69 168.93 [Xe]4f13 6s2 Thulium
Yb 70 173.04 [Xe]4f14 6s2 Ytterbium
Lu 71 174.967 [Xe]4f14 5d1 6s2 Lutetium
Other notable elements
Eu2+
Ce4+
Sc3+ 21 44.9559 [Ar]3d1 4s2 Scandium
Y3+ 39 88.9059 [Kr]4d1 5s2 Yttrium
Ca2+ 20 40.078 [Ar]4s2 Calcium
Mn2+ 25 54.938 [Ar]3d5 4s2 Manganese
Sr2+ 38 87.62 [Kr]5s2 Strontium
Th4+ 90 232.0381 [Rn]6d2 7s2 Thorium
U4+ 92 238.0289 [Rn]5f3 6d7s2 Uranium
1
:see [1].

permits either Ce3+ or Ce4+ , with electron configurations and U4+ have smaller ionic radii than Ln3+ [1, 2]. The ionic
corresponding to [Xe]4f1 and [Xe], respectively. radius of O2− is 140 pm and corresponding octahedral (CN
The influence of f orbitals on the chemical attributes 6) and cubic (CN 8) cavities accommodate ionic radii from
of the REEs is readily apparent by observing the regular 58 to 102.5 pm and greater than 102.5 pm, respectively.
decrease in the ionic radii on progression from La to Lu
(Table 1). The so-called “Lanthanide Contraction” arises
because of the incomplete electric field shielding by the f 2. Rare Earth Element Rock and
orbitals and unit increases in nuclear charge on transition to Sediment Abundances
greater atomic numbers. The importance of the lanthanide
contraction phenomena is revealed in the greater chemical Chondrite meteorites are generally considered to be com-
affinity for hydrolysis and greater stability of selected com- posed of igneous materials that have not had an extensive
plexes on progression from the LREEs to the HREEs. LREEs history of melting and recrystallization, thus the REEs
are the light rare earth elements, comprised of the elements composition is considered to be representative of magma
La to Eu, whereas HREEs are the heavy rare earth elements, prior to any fractionation processes. Historically, igneous
comprised of the elements Gd to Lu. petrologists have used chondrite REEs concentrations to
The ionic radius of any cationic species is experimentally index or “normalize” rock samples (REEs ratio of the sam-
determined and is largely dependent on its atomic number, ple/chondrite) to estimate the type and extent of magmatic
oxidation state, the coordination number (CN), and the processes responsible for lithosphere evolution.
radius of the anionic species. The ionic radii of REEs having Rock REEs concentrations vary markedly with rock type
octahedral coordination (CN 6) ranges from 103.2 pm for La and source area. In general, most parent materials have
to 86.1 pm for Lu (pm = picometer = 10−12 meters), whereas REEs compositions ranging from 0.1 to 100 mg/kg, thus the
the ionic radii of the REEs having cubic coordination (CN 8) REEs actually have moderate concentration ranges compared
ranges from 116.0 pm for La to 97.7 pm for Lu. The ionic with many other trace elements. Rhyolites and granites
radii for Ln3+ species are generally smaller than the ionic typically have greater REEs concentrations than basalts
radii for K+ , Rb+ , Cs+ , and Ba2+ , whereas Mn2+ , Y3+ , Th4+ , and peridotites (Figure 1), with the LREEs concentrations
ISRN Soil Science 3

160 100

REE concentrations (mg/kg)

80
120

60
(mg/kg)

80
40

40 20

0
0 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Loess
MORB Sandstone
BC horizons of Menfro series
Rhyolite Limestone
Figure 1: REEs concentration values for an average rhyolite, mid- Figure 3: REEs concentration values for a typical loess. Loess REEs
ocean ridge basalt, sandstone and limestone. Concentration values concentration values were reported in Kabata-Pendias [4], whereas
were reported in Kabata-Pendias [4]. the REE concentrations from two soils of the Menfro (Missouri)
series are unpublished data by the author.

100

80 the REEs distribution of the average of two BC horizons from

pedons of the Menfro series (Typic Hapludalfs) located in
60 deep Peoria Loess along the Mississippi River in Missouri.
(mg/kg)

The minerals apatite and zircon are frequently the domi-

40 nant REEs-bearing trace minerals in soils, thus their REEs
contribution may substantially influence the whole soil REEs
20 concentrations [2].
The Oddon-Harkins rule states that an element with an
0
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu even atomic number has a greater abundance than the next
element in the Periodic Table. The REEs frequently obey
PAAS the Oddon-Harkin rule; such that, Ce (atomic number =
NASC 58) typically has a greater concentration than Pr (59) and
Figure 2: REEs concentration values for Post-Archean Australian culminating with Yb (70) having a greater concentration
Average Shale (PAAS) and North American Shale Composite than Lu (71). Observation of the Chondrite, PAAS, NASC,
(NASC). Concentration values were reported in McLennan et al. [5] and other parent material elemental compositions reflect the
with original citations in Taylor et al. [6] for the PAAS and original Oddon-Harkin rule.
citations in Gromet et al. [7] for the NASC.

3. Rare Earth Element Abundances in

markedly greater than the HREEs concentrations. Rare earth Primary Minerals
element concentrations have been routinely determined
using instrumental neutron activation analysis [3]. Primary minerals are minerals formed at the time of rock
Argillaceous sediments and shales typically have greater formation and have not been chemically altered by supergene
REEs concentrations than limestones and sandstones or weathering processes. REE compositions of primary
(Figure 1). As with igneous materials, sedimentary materials minerals show dramatic element abundance differences and
typically exhibit greater LREEs concentrations than HREEs many primary minerals show enrichment or depletion of
concentrations. selected REEs or groupings of the REEs. The mineral apatite
Important reference standards for sediments include is generally enriched in the LREEs and the mineral zircon is
the Post-Archean Australian Shale (PAAS) and the North generally enriched in the HREEs. Zircon is commonly con-
American Shale Composite (NASC) (Figure 2). The LREEs sidered highly resistant to weathering, thus a large portion
typically exhibit greater abundances than the HREEs. of the HREE pool may reside in zircon lattice positions and
Loess is a Pleistocene-Holocene aged silty-textured sedi- are not amenable to interhorizon transport. Table 2 lists un-
ment deposited by wind from major river valleys, primarily published instrumental neutron activation analysis of micro-
in North America, Europe-Russia and China. Typical loess cline, oligoclase, hornblende, and augite to illustrate selected
REEs distributions were reported by Kabata-Pendias [4], REE concentrations.
showing that the LREEs concentrations were greater than A brief listing of some common REE-bearing minerals,
those of the HREEs (Figure 3). Also included in Figure 3 is showing REE lattice substitution, are in Table 3.
4 ISRN Soil Science

Table 2: Instrumental neutron activation analysis of selected REEs in selected minerals.

Mineral La Ce Nd Sm Eu Tb Yb Lu
mg/kg
Microcline bdl 20 23 bdl 0.2 bdl bdl bdl
Oligoclase bdl 27 49 bdl 1.7 1.1 0.6 0.17
Hornblend 5 7 31 3.2 0.7 bdl 1.2 0.05
Augite 36 39 57 4.4 0.4 1.3 5.1 1.25
Detection limit 1 3 10 0.5 0.2 0.5 0.5 0.05
bdl: below detection limit.
Unpublished analysis by instrumental neutron activation analysis by authors.

Table 3: Common minerals having rare earth element (REE) substitution.

Mineral Formula Comments

Fluorite CaF2 Y and Ce replace Ca
Allanite (Ce, Ca, Y)2 (Al, Fe2+ , Fe3+ ) 3 (SO4 )3 OH

Sphene CaTiSiO5 Y and REE replace Ca

Zircon ZrSiO4 Y and HREE replace Zr
Apatite A5 (XO4 )3 (F, OH, Cl); A = Ca,Be,Ce,Pb Y and REE replace Ca
Monazite (CeLa)PO4
Xenotime YPO4 REE replaces Y
Rhabdophane (Ce, La)PO4 REE replaces La
Bastnaesite La(REE)-fluorocarbonate
Reported in Clark [8].

4. Rare Earth Element Abundances in 60

Secondary Minerals
50
REE concentrations (mg/kg)

Secondary minerals are minerals formed in the near surface

environment by precipitation reactions and incongruent or 40 Average soil
congruent weathering reactions. In some cases, REEs are
30
involved with isomorphic substitution or undergo adsorp-
tion reactions with phyllosilicates or oxyhydroxides. REE-
20
phyllosilicate interactions have been investigated, with the
majority of studies reporting that the REE elements form 10
weak outer-sphere complexes (exchangeable) at pH levels in
acidic environments and an increasing degree of inner sphere 0
complexes at pH levels approaching 5 and transitioning to La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
more alkaline soil environments [9–17] in selected alluvial
Albaqualfs in Missouri accumulated Ce and revealed a Figure 4: REE concentration values for an average soil. Concentra-
positive Ce anomaly, suggesting that alternating conditions tion values were reported in Kabata-Pendias [4].
of oxidation-reduction were important for Fe-Mn nodule
synthesis and Ce incorporation.
Kronberg et al. [18] investigated Amazon deep-sea fan
5. Rare Earth Element Abundances in Soil
deposits and inferred that intense chemical weathering and
erosion in adjacent mountainous regions were responsible Rare earth element abundances in soils are influenced
for the large REE sediment concentrations. Condie [19] by their parent materials, texture, weathering history and
and Nesbitt and Markovics [20] previously proposed that pedogenic processes, organic matter contents and reactiv-
the continental weathering and fluvial systems operate to ity, and anthopogenic disturbances. In a review of trace
accumulate REE in depositional basins. element occurrences, Kabata-Pendias [4] complied mean
Precipitation reactions with fluoride, phosphate, and REE concentrations of selected parent materials and surface
carbonate may yield a variety of secondary REE minerals [8]. horizons of soils. For soils, the LREE concentrations are
Cerianite (CeO2 ) may form in oxidizing soil solutions [21– generally greater than the HREE concentrations and the REE
27]. [8] have documented an impressive listing of primary concentration distribution typically obey the Oddon-Harkin
and secondary minerals having REE incorporation. rule (Figure 4).
ISRN Soil Science 5

100 9
90 REE + H2 O = REEOH + H+
80 Hydrolysis
8.5
70
Eu speciation (%)

− log K (25 C)
60
50 8
40
30
20 7.5
10
0 7
4 6 8 10 12 14
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
(pH)

Eu Eu (OH)3 Figure 6: REE hydrolysis constants (Values reported in [30]).

Eu (OH) Eu (OH)4
Eu (OH)2
100
Figure 5: Aqueous hydroxyl speciation of Eu (III) over a pH inter- 90
val. The Eu speciation involved concentrations without recourse to
80
activity coefficients and overall formation quotients from Baes and
70
Eu speciation (%)
Mesmer [28].
60
50
The REE concentrations in the soil environment are es- 40
sentially the weighted mean of the REE concentrations of the 30
minerals in the soil and the associated REE-bearing miner- 20
al abundances. In most soil cases, the whole soil REE con- 10
cen-trations are more directly related to the presence of a few 0
trace minerals, such as apatite and zircon. REE associations 5 6 7 8 9 10
with soil organic matter, phosphate precipitates, phyllosili- (pH)
cate and oxyhydroxides may be important in discerning REE
soil migration and availability; however, the REEs in youth- Eu
Eu (CO3 )
ful soils having little weathering of the REE-bearing minerals Eu (CO3 )2
usually reveal little REEs mobility.
Figure 7: Aqueous hydroxyl and carbonate speciation of Eu (III).
The Eu speciation involved concentrations without recourse to
6. REE Chemistry and Soil Pedogenic Processes activity coefficients and overall formation quotients from Baes and
Mesmer [28], carbonate complexation constants from Luo and
The hydrolysis of Ln3+ species has been extensively investi-
Byrne [36], and acid dissociation constants for carbonic acid and
gated and numerous authors have published hydrolysis data bicarbonate from Essington [37]. Author performed calculations
[16, 17, 28–32]. For example, Eu3+ will undergo hydrolysis using MinteqA2 [38].
to produce Eu(OH)2+ , Eu(OH)2 + , Eu(OH)3 and Eu(OH)4 − ,
having log K◦ constants log K11 ◦ = −7.64, log K12 ◦ = −15.1,
log K13 ◦ = −23.7, and log K14 ◦ = −36.2, respectively [32].
Europium hydrolysis speciation as a function of pH illus- where Ln− is an inorganic ligand with n ionic charge and y
trates that the Eu3+ species is the dominant species in acidic is the stoichiometric coefficient. Common inorganic com-
and near-neutral pH environments, whereas the Eu(OH)2 + , plexing species with Ln3+ include NO−3 , Cl− , F− , SO24− ,
Eu(OH)3 , and Eu(OH)4 − species are the dominant Eu CO23− , and HPO24− . Carbonate and dicarbonate complexes
species in alkaline and strongly alkaline pH environments exist, with carbonate complexes more prevalent in the LREEs
(Figure 5). The hydrolysis speciation of any Ln3+ species is and dicarbonate complexes more prevalent in the HREEs
similar to that of Eu3+ , with a necessary understanding that [16, 29, 33, 34] Luo and Byrne, 2000 [35]. For illustration
the relative stabilities of the various REE hydrolytic species purposes, the Eu speciation involving aqueous equilibrium
are more stable on transition with increasing atomic number carbonate complexes with atmospheric CO2 concentrations
across the Lanthanide series (Figure 6). are displayed in Figure 7.
Complexation of the REE elements involves coordination The complex constants for the formation of
with primarily anionic species and typically is expressed as: REE(HCO3 )2+ and REE(HCO3 )+2 are displayed in Figure 8.
The complexation constants show increasing stability on
progression from La to Lu, with Gd and Nd showing slight
Ln3+ + yLn− = LnLy (3− yn) , (1) trend departures.
6 ISRN Soil Science

10 140

9 120
8 100
7
− log K (25 C)

80

(µg/kg)
REE complex with
6 HCO3 and 2HCO3
60
5
40
4
20
3
0
2 La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Endoaqualfs
HCO3 Eutrochrepts
2HCO3
Figure 9: Water extraction of REE from Endoaqualfs in Missouri
(mean of 27 observations, coefficient of variation is less than five
Figure 8: REE complex constants for HCO3 and 2 HCO3 (values
percent) and Eutrochrepts in Missouri (mean of 24 observations,
reported in [36]).
coefficient of variation is less than five percent).

Millero [29] and Gramaccioli et al. [39] observed that

7. Rare Earth Elements and Soil Development:
REE-fluoride complexes obtained greater stability on tran- Case Studies
sition from La to Lu. Banfield and Eggleton [40] emphasized
The importance of the REEs rests with their “signature,”
the importance of REE-phosphate precipitates in limiting
which may be defined as either the actual REE concentrations
the mobility of the REE in soils and sediments. Cetiner et
or their normalized concentrations displayed according to
al. [41] detailed the REE solubility when phosphate was the
their atomic number. Analysis of the REE signatures typically
determining anion.
involves the summation of the total concentrations of all
Organic acids have been implicated as major weathering of the REEs (ΣREE) and evidence of fractionation, that is,
agents and organic acid complexation may be a major LREE and HREE ratios, La/Yb ratios, Nd/Sm ratios, and the
pathway for interhorizon REE transport [42, 43]. Common presence of Ce or Eu anomalies. REE signatures have been
organic complexes involving the REE include both lower compared to reveal (1) lithologic discontinuities [65–67], (2)
molecular weight organic acids and naturally occurring the presence of aeolian or anthopogenic additions [59, 68–
higher molecular weight fulvic and humic acids [20, 24, 44– 70], (3) estimates of the weathering intensities and elemental
53] Lead et al. [54]. Tyler and Olsson [55] reported that loss rates of soils [20, 23, 24, 44, 45, 47, 71–78]), and (4)
46 to 74% of the REE extracted from the aqueous phase of oxidation-reduction conditions in soil [79].
a Swedish Cambisol were associated with dissolved organic REEs in soils were originally assumed to be immobile.
carbon. As with the inorganic REE complexes, organic REE Nesbitt [80] in a pioneering study involving soils developed
complexes tend to show greater stability for the HREEs than in granodiorite proposed that CO2 and organic matter bear-
the LREEs [33, 51]; however, Ohlander et al. [56] and also ing soil waters percolated through the soil profiles, removing
Land et al. [47] reported greater stability for the LREEs than the REEs as carbonate complexes. The REEs were removed
the HREEs. from the percolating soil water in deeper, less weathered
Cao et al. [57] and Tyler and Olsson [58] observed that and less acidic granodiorite materials as exchangeable,
the strength of REE-organic complex bond strengths are adsorbed or precipitated phases. The HREEs were enriched
greater with increasing soil pH. Nikonov et al. [59], Dupre et in the deeper material to a greater degree than the LREEs,
al. [60] and Gu et al. [49] each proposed that immobile soil promoting the concept that the REEs may not act uniformly
organic matter fractions have a range of complexing bond and that differences in REEs reactivity related to atomic
strengths that limit REE mobility. Rare earth element uptake number results in REE segregation (REE fractionation).
by plant roots has been documented ([61–64]). Duddy [81] proposed that REEs accumulate in the
Aide (unpublished research) employed a 45 mμ filtered deeper portions of soils developed from volcanic rocks. Sub-
water leach extraction on a series of Endoaqualfs (poorly sequently, Nesbitt and Markovics [20] investigated soil pro-
drained Alfisols) and Eutrochepts (somewhat poorly- file development in granodiorite in Australia and showed
drained Inceptisols) in southeastern Missouri to show REEs that the REE and many transition metals and metalloids ac-
availability (Figure 9). Cerium was consistently the most cumulated in the deeper and less-weathered portions of the
abundant REE leached from the soils, followed by La and soil profiles. They effectively documented that REE leaching
Nd. The LREE had greater leachate concentrations than the and surficial erosion combined to promote the continuous
HREE. REE compliance with the Oddon-Harkin’s rule was cycling of the REE to deeper soil regions.
consistently observed. Aide et al. [82] investigated a series of Ultisols in southern
ISRN Soil Science 7

70 500

60 Irvington-Ultisol Lithic Haplustolls

400
50
REE (mg/kg)

REE (mg/kg)
40 300

30 200
20
100
10

0 0
Ce Nd Sm Eu Tb Yb Lu Lu La Ce Nd Sm Eu Tb Yb Lu

Ap Rock
Btvx2 Soil
2Btg
Figure 11: REE concentrations of a Lithic Haplustoll (Brewster
Figure 10: REE concentration values for the Ap, E, and Btvx2 hori- series in Texas) showing parent material-soil similarity.
zons of a soil of the Irvington series.

subsequent precipitation of REE-phosphate phases in the

Mississippi having plinthite (Figure 10). The element Ce has deeper soil horizons.
a greater concentration across the lithologic discontinuity Gouveia et al. [72] investigated the weathering of Por-
indicating either an inherited REE difference or preferential tuguese soils developed in granite, resulting in a soil-sa-
Ce transport across the lithologic discontinuity. prolite-weathering rind-fresh rock sequence. Chondrite-
Aide and Smith [83] investigated Paleustoll soils in south normalized REE signatures of the fresh rock indicated a
central Texas and observed that the LREE concentrations pronounced LREE abundance and a positive Eu anomaly.
Compared to the near-surface horizons, the upper portion of
were greater in the argillic horizons than the surface horizons
the saprolite demonstrated a decreased REE content, whereas
and proposed that the clay fraction in the argillic horizon
the deeper portion of the saprolite showed REE accumu-
accumulated the LREEs. In a similar study, Aide et al.
lation. The sand fraction showed a low REE concentration
[70] investigated Lithic Haplustolls in the Chisos Mountain
attributed to the presence of quartz sand and exhibited a
of Texas and observed that the host rock and the fine
positive Eu anomaly attributed to the presence of plagioclase.
earth fraction exhibited similar REE distribution patterns The clay fraction demonstrated greater REE concentrations
(Figure 11). In this study, the concentrations of the LREE and a negative Eu anomaly, inferring that soil weathering and
were greater than the HREE and both the soil and host rock clay-REE adsorption reactions augmented the clay fraction’s
exhibited a negative Eu anomaly, suggesting that the soil REE REE concentrations.
signatures were inherited from the host rock. Aide et al. [65]
Aide and Pavich [84] investigated Alfic Haplorthods in
in Missouri investigated Typic Paleudalfs developed in loess
northern Wisconsin using instrumental neutron activation
over volcanic residuum and reported that the greater REE
analysis for total REE concentrations (Figure 12). An aqua
concentration in the near surface horizons were attributed regia digestion procedure recovered nearly as much of the
to the thin loess mantle, thus assisting in the recognition LREE pool as instrumental neutron activation analysis;
of parent material differences. In a companion manuscript, however, the aqua regia digestion only marginally recovered
Aide et al. [66] used Ti as an immobile index to indicate that the HREE pool. Aide and Pavich proposed that apatite was
the REE have been partially depleted from the soil profiles the major repository for the LREE and zircon was the major
relative to the host rock. repository for the HREE. Sodium pyrophosphate extraction
MacFarlane et al. [73] investigated paleosols in west- of the REE only recovered a small portion of the aqua regia
ern Australia developed on contrasting basalt flows. They digestion pool, suggesting that that organic fraction was not
inferred that REE migration promoted the downward move- the dominant REE soil fraction.
ment of the REE to the middle portion of the paleosols REE fractionation was demonstrated in Swedish Spo-
and that the relative movement of the LREE was greater dosols developed in granite till [47]. Land’s investigative team
than that for the HREE. Prudencio et al. [44] investigated documented that the E horizons were REE depleted, when
soil development on alkali basalts in the Lisbon Volcanic normalized against the granite till, and that REE depletion
Complex in Portugal. REE concentrations were greater in increased on progression from the LREEs to the HREEs. The
the deeper argillic horizons than the overlying soil horizons Bs horizon was REE depleted, but not to the extent of the
and the REE concentrations were appreciably greater in the overlying E horizon. Selective extractions demonstrated that
clay separate. They further proposed that apatite weathering the crystalline Fe-oxyhydroxide and labile organic fractions
in the near surface acidic horizons mobilized the REE, with accumulated the HREE to a greater extent than the LREE,
8 ISRN Soil Science

50 Plant uptake
Padus-Spodosol
40
Ap REE SOM-REE
REE (mg/kg)

30
Leaching
20 B
REE
10 Eluviation-
Illuviation Adsorption
0
La Ce Nd Sm Eu Tb Yb Adsorption on clay
and oxyhydroxides
A Precipitation
E
Bs
Figure 13: An illustration of the potential pathways for REE
Figure 12: REE concentration values for the A, E, and Bs horizons migration and sequestration.
of the soil of the Padus series.

consisting of a yellow clayey matric overlying an indurated

whereas the soil organic matter fraction representing humic ferruginous horizon, were REE depleted based on parent
and fulvic acids preferentially accumulated the LREE. rock normalization. The deeper basal saprolite demonstrated
In Sweden, Ohlander et al. [56] observed that weathering zones for the accumulation of Ce and other LREE. The HREE
of a series of Typic Haplocryods developed in till has depleted were depleted in the basal saprolite material. The LREE
the REE’s in E horizons, with the degree of depletion greater elements were proposed to be precipitated as rhabdophate
(LREE-PO4 -nH2 O) and cerianite (CeO2 ). Xenotime was the
for the LREE. The Bs horizons of these soils showed REE
dominant primary mineral acting as a repository for the
accumulation at some sites, whereas other locations showed
HREE. Acidic groundwater extracted from the basal saprolite
REE depletion. They further proposed that hornblende, epi-
demonstrated a high LREE content and a negative Ce anom-
dote, apatite, allanite, and monazite release REEs on weath-
aly, reflecting the REE composition of the parent material.
ering and that the clay fraction, with its greater oxyhydrox-
In central Uganda, Brown et al. [77] used Th as an indexing
ide and adsorbed organic matter content, may be an impor- element for highly weathered soils to show REE depletion
tant adsorptive repository for the REE, thus inhibiting their with little LREE/HREE fractionation.
removal from the soil profile. Tyler and Olsson [58] showed Oliva et al. [48] studied weathering processes in a
that the majority of the REEs were 40 to 50% removed from small Cameroon watershed containing lateritic landscapes.
the A and E horizons of a Swedish Haplic Podzol. The majority of the chemical weathering in the watershed
Braun and Pagel [45] investigated REE migration in was located in basin positions having restricted drainage.
Cameroon lateritic soil profiles developed in Precambrian The hydromorphic soils exhibited organic-rich over sandy-
syenite. The soil profiles generally consisted of four layers: textured horizons which were superimposed on a clayey and
(1) an surface layer consisting of loose, nodular ferruginous mottled section having an abundance of goethite. The deeper
materials having indurated hematite nodules, (2) a pedoplin- clayey layer exhibited an accumulation of LREE and dis-
thite (iron crust) layer, (3) a mottled clay layer possessing played little evidence of a Ce anomaly. The authors pro-
plinthite, and (4) saprolite with whitish seams of clayey ma- posed that organic acids promoted mineral dissolution and
terial enclosing the sandy-textured remains of syenite boul- the subsequent transport of Al, Fe, Ti, Zr, and the REEs.
ders. Analysis of fresh syenite rock revealed that 70% of The REEs were assumed to have interacted with phosphate
the REE pool, 40% of the HREE pool, and 50% of the to limit their transport and soil profile removal.
Th pool was contained in allanite, epidote, titanite, and
apatite. Thorium was the least mobile element, forming the
8. Pathways for REE Migration in Soil
relatively inert mineral thorianite (ThO2 ). Long-term weath-
ering of these minerals in the Fe-rich upper soil horizons Pathways for REE migration are numerous, involving (1)
(layers 1 and 2) resulted in REE depletion relative to Th plant uptake, (2) erosion, (3) leaching of REE-inorganic
as an indexing element, whereas the deeper clay rich hori- complexes in percolating water, (4) organic complexation
zons and saprolite showed REE accumulation. The LREE which may result in either mobilization or immobilization of
were precipitated as florencite (REE-phosphates), except that the REEs, (5) lessivage (eluviation-illuviation of clay with co-
Ce was oxidized and precipitated as cerianite (CeO2 ). The adsorbed REE’s, (6) removal of REE’s from percolating water
whitish seams demonstrated a positive Ce anomaly, con- attributed to precipitation reactions, and (7) adsorption of
sistent with cerianite precipitation. REE’s by inorganic colloids (phyllosilicates and oxyhydrox-
Braun et al. [24] in Cameroon used Th indexing to ides) (Figure 13). An important aspect of the REE’s is their
study REE migration in lateritic soils. The upper horizons, similar soil chemistry; however, small differences in their
ISRN Soil Science 9

hydrolysis and inorganic-organic complexation constants Ca-montmorillonite and Na-illite. Part 1: batch sorption and
and inherent differences in the weathering susceptibility of time-resolved laser fluorescence spectroscopy experiments,”
the various REE-bearing minerals allow fractionation and Geochimica et Cosmochimica Acta, vol. 69, no. 23, pp. 5393–
differential migration potential. The real value of the REE’s 5402, 2005.
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