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Procedia Earth and Planetary Science 17 (2017) 758 – 761

15th Water-Rock Interaction International Symposium, WRI-15

The role of fluids in the formation of rare earth element deposits

Philip L. Verplancka,1
a
U.S. Geological Survey, M.S. 973 Denver Federal Center, Denver, CO 80225, U.S.A.

Abstract

Fluids play an important role in the formation of many rare earth element (REE) deposits. Groundwater and hydrothermal fluids
can transport these elements and with changes in fluid composition or properties, the REEs can be removed from solution by
adsorption or precipitation of REE-rich minerals. Currently, REEs are primarily produced from two types of ore deposits, ion
adsorption clay deposits (located in southern China) and carbonatites. Ion adsorption clay deposits in southern China form by
lateritic weathering of underlying granites. Groundwater is responsible for the mobilization, transport, and deposition of the
REEs in forming these ore deposits. Carbonatites are a relatively rare type of igneous rock that contain the highest concentrations
of REEs of any igneous rocks. Ore-grade REE enrichment in carbonatites can result from crystallization of REE mineral phases
directly from the magma or by hydrothermal processes. One carbonatite-related REE ore deposit, the Mount Weld deposit
(Australia), was formed by lateritic weathering of the underlying carbonatite.
© 2017
2017Published
The Authors. Published
by Elsevier B.V. by
ThisElsevier B.V.
is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of WRI-15.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
Keywords: groundwater; hydrothermal fluid; rare earth element; laterite

1. Abstract

Rare earth elements (REEs) are not as rare in nature as their name implies, but economic deposits are not
common and few deposits have been large REE producers. In the past 20 years, demand for REEs has increased
dramatically because of their applications including chemical catalysts, metal alloys, glass polishing, and permanent
magnets. Because of their unique properties, REEs are essential for use in high tech devices including smart phones,
digital cameras, computer hard disks, fluorescent and light-emitting-diode (LED) lights, flat screen televisions,
computer monitors, and electronic displays.
The REE group is composed of 15 elements that range in atomic number from 57 (lanthanum) to 71 (lutetium),
and yttrium (atomic number 39) is commonly regarded as a REE because of its chemical and physical similarities

* Corresponding author. Tel.: +1-303-236-1902; fax: +1-303-236-3200.

E-mail address: plv@usgs.gov

1878-5220 © 2017 Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of WRI-15
doi:10.1016/j.proeps.2017.01.014
 Philip L. Verplanck / Procedia Earth and Planetary Science 17 (2017) 758 – 761 759

and affinities. Scandium (atomic number 21) is chemically similar to, and thus sometimes included with, the REEs,
but it does not occur in economic concentrations in the same geological settings as the other REEs and will not be
discussed further. Rare earth element deposits are generally enriched in either light REEs (LREEs; La-Gd) or heavy
REEs (HREEs; Tb-Lu).
The present global production of REEs comes from only a few sources. Two ore-deposit types account for the
vast majority of world’s REE production. A few carbonatite-related deposits provide the world’s LREEs, and
numerous small ion adsorption clay deposits in southern China provide the world’s production of HREEs.
Carbonatites are a relatively rare type of igneous rock composed of greater than 50 vol.% primary carbonate
minerals, dominantly calcite and/or dolomite, and contain the highest concentrations of REEs of any igneous rocks.
Chondrite-normalized REE patterns for carbonatites display extreme LREE enrichment, no Eu anomaly and a steep
pattern with a negative slope. Ore-grade enrichment of REEs in carbonatites can occur by primary magmatic
crystallization of REE-rich mineral phases or by late-stage fluid mobilization and consequential REE-phase
crystallization. In one deposit currently being mined, Mount Weld, the REE ore-grade enrichment is due to lateritic
weathering of an underlying carbonatite. The second deposit type, ion adsorption clay deposits in southern China,
form by tropical weathering of granites where the REEs are released to solution from minerals within the granite and
a significant fraction are adsorbed on to clays in the weathered zone. Chondrite-normalized REE patterns of these
deposits vary due to a number of factors that will be discussed in the following sections. Compared to other REE
deposits, these deposits are relatively low grade but are economic to mine because they can be enriched in the more
valuable HREEs and are relatively inexpensive to mine.
Fluids can play a significant role in ore-grade enrichment of REEs in both carbonatite and ion adsorption clay
deposits. This paper will review the fluid-driven processes involved in REE deposit genesis. Similar to many metals,
the behavior of REEs in aqueous solutions can be described as a competition between the formation of stable
aqueous complexes and the tendency of REEs to partition to solid phases either by adsorption or (co)precipitation.
Solution chemistry plays an important role with the dominant inorganic ligands being carbonate, phosphate, sulfate,
hydroxide, chloride, and fluoride. Other factors that may affect partitioning between solid and aqueous phases
include: pH, temperature, redox conditions, and the composition of solid phases.

2. Discussion

2.1. Hydrothermal fluid-derived REE enrichment in carbonatites

Carbonatites and certain alkaline igneous suites of rocks are enriched in REEs, some of which have been mined
or are in the advanced exploration stage. Ore-grade REE enrichment due to orthomagmatic/hydrothermal fluids is
evident in a variety of these locations. The requirements for achieving ore-grade REE enrichment are an adequate
endowment of REEs in the initial magma and evolution of the magma such that the REEs are concentrated. In
general, these magmas evolve by fractional crystallization and the gravitational separation of early formed
crystals1,2. Carbonatite and other alkaline magmas may contain a variety of volatile components that include CO 2,
H2O, Cl, F, and S. As crystallization progresses, these components become enriched in the residual magma along
with various incompatible elements and can exsolve into a separate fluid phase. Fluid inclusions and fenite alteration
(alkali metasomatism) provide clear evidence for the separation of a volatile-rich fluid phase. Depending on the
composition of the magma and its evolution, primary REE-bearing minerals can crystalize directly from the magma,
as is the case for bastnäsite at the Mountain Pass deposit, or the REEs can remain in the magma behaving as
incompatible elements and partition into the fluid phase. REE minerals crystalizing from these late-stage fluids tend
to be fluorocarbonates (bastnäsite, parisite, and synchysite, Fig. 1A) and phosphates (monazite and apatite, Fig. 1B).
The fluorocarbonates are generally described as very fine-grained (1-100 µm), forming syntaxial intergrowths as
bundles, clusters, or aggregates of radiating needles. The crystals may form in miarolitic cavities or at the expense of
primary minerals. The origin of these REE mineral phases is commonly attributed to the late-stage magmatic-
hydrothermal phase of carbonatite evolution. The REEs may behave as incompatible elements that partitioned into
this phase during carbonatite evolution, or they could have been remobilized from earlier formed mineral phases.
760 Philip L. Verplanck / Procedia Earth and Planetary Science 17 (2017) 758 – 761

The initial magma composition and petrogenetic evolutionary path both control the composition of the
crystallizing phases, and thus the composition of the residual melt. The exsolution of a fluid phase from the melt
depends not only on the melt composition, but also on pressure and temperature variations. Fluid inclusion

Fig. 1. SEM backscattered electron images of REE phases in in the Elk Creek carbonatite. (A) REE fluorocarbonates; (B) Monazite infilling.

studies provide general characteristics of fluid phases exsolved from carbonatite melts and document the presence of
H2O, CO2, alkalis, and ligands, including F-, OH-, Cl-, SO42-, CO32-, and PO42-. These ligands play a key role in the
disposition of REEs in magmatic and aqueous systems. Mineral saturation controls the removal of REEs from the
aqueous phase and is controlled by changes in pressure, temperature, pH, and chemical composition.

2.2. Ore-grade REE enrichment in weathered deposits

Lateritic weathering is an important process in the formation of some REE deposits including the ion adsorption
clay deposits in south China and the Mount Weld deposit in Australia. Factors controlling the degree of lateritization
include climate, topography, length of time exposed in a stable environment, and bedrock composition. Optimal
conditions for the formation of substantial lateritic zones include a topography that allows the entrapment of newly
formed residual minerals and a tectonically stable region where denudation rates are low and the weathering profiles
are preserved. Lateritization is driven by the interaction between infiltrating groundwater and the bedrock it contacts.
Physical properties, such as cleavage and porosity, are important because they control the amount of mineral
surfaces available for interaction. Aqueous properties, such as temperature, acidity, redox potential, and dissolved
constituents affect the type of chemical reactions that will occur and their rate. The mineralogy of the rock being
weathered not only plays a role in the rate of weathering, but also influences the composition of the aqueous phase,
which in turn can control the degree to which REEs are released to the downward moving fluid and the formation of
secondary phases. In general, Ca, Mg, K, and Na partition to the aqueous phase and are then leached from the
system. In contrast, Fe is quite reactive, as can be Al, and these elements end up in secondary phases, including
goethite, hematite, gibbsite, and various clay minerals.
The ion-adsorption type REE deposits in south China (Jiangxi, Guangdong, Fujian, Zhejiang, Hunan, Guangx,
and Yunnan provinces) are generally 6 to 10 m thick, but can reach 30 m, and form above granites. The thickest part
of the profiles tends to be at the top of hills and ridges, and the thickness decreases downslope 3. This area is
characterized as a temperate climate region that receives an average annual rainfall of 1500-2000 mm and has an
annual temperature of 18°-21°C4. The denudation rate is low because it is a stable tectonic area and the topography is
relatively gentle. The underlying granites that form the REE deposits are generally biotite and muscovite granites
characterized by metaluminous to weakly peraluminous compositions and low P 2O5 contents5. These granites can
either be LREE or HREE enriched, and the chondrite-normalized REE patterns of the resulting weathered zone
generally reflects the character of the underlying granite3. The HREE-rich granites are highly differentiated (SiO2
>~75%) muscovite granites3. In the granites, the REEs initially were primarily hosted in accessory mineral phases
including allanite, titanite, monazite, zircon, and xenotime. A deuteric alteration event altered the magmatic allanite
and titanite to secondary REE mineral phases, which subsequently host the REEs in the deposits 3,5.
Downward percolating groundwater near the surface is slightly acidic and breaks down susceptible REE-bearing
mineral phases partitioning the REEs into the aqueous phase. Ce can be oxidized in the shallow environment and
precipitate either with Mn or as cerianite (CeO 2). REEs move down gradient in groundwater as dissolved
constituents or associated with colloidal particles. A fraction of REEs leave the system laterally. One key to higher
 Philip L. Verplanck / Procedia Earth and Planetary Science 17 (2017) 758 – 761 761

REEs concentrations in the product is when the groundwater flow has restricted lateral movement. Removal of REEs
from solution occurs by sorption and precipitation driven by solution chemistry and solid phase composition (pH,
ligand concentrations, mineral saturation, redox conditions, temperature, solid phase chemistry and composition). In
general, as the groundwater moves downward, the pH increases due to mixing or water-rock interactions, and the
REEs partition onto solid phases, adsorbing onto clay particles including kaolinite and halloysite or forming
secondary REE mineral phases. This “ore zone” has grades ranging from 140 to 6,500 ppm (typically ~800 ppm)5.
These deposits are relatively inexpensive to mine either by shallow pits or in situ leaching.
The Mount Weld REE deposit in western Australia is hosted in a lateritic sequence that reflects supergene
enrichment of the underlying carbonatite complex. The laterite sequence consists of a supergene enrichment zone as
thick as 90 m, which is located above a 3- to 30-m-thick residual zone that overlays the unweathered carbonatite.
The underlying calcite carbonatite is composed of calcite with minor magnetite, apatite, olivine, biotite, and
pyrochlore. Rare earth element-rich minerals include calcite, apatite, and possibly pyrochlore 6. The chondrite-
normalized REE pattern of the carbonatite (Fig. 2) is typical of an average carbonatite, with LREE enrichment, no
Eu anomaly, and HREE depletion. In the laterite, secondary monazite is the dominant REE-bearing phase in the
laterite ore and typically is fine grained and can occur as pseudomorphs after apatite and rhabdophane. In addition,
cerianite and crandallite subgroup minerals can be host phases for REEs. Gangue minerals include goethite and
hematite, with minor calcite, cryptomelane, dolomite, hollandite, kaolinite, maghemite, montmorillinite, magnetite,
pyrochlore, ilmentite, and rutile, and traces of quartz, barite, anatase, and vermiculite 7,8.
The chondrite normalized REE pattern of the laterite displays extreme LREE enrichment compared to the
underlying carbonatite (Fig. 2). Oxygenated groundwater in the near-surface environment can be slightly acidic. This
water interacts with primary minerals, such as calcite, dolomite, and apatite, to mobilize Ca and Mg and liberate
REEs. Other elements, such as Al, Fe, P, K, and Na, are also released from these and other phases. In this
environment, dissolved ligands likely available to complex REEs include phosphate, carbonate, fluoride, and
chloride. Note that lateritic mineralization on a carbonatite substrate does not require the presence of early
crystallized, discreet REE-rich minerals, like in a granitic terrain, because a substantial fraction of the REEs can be
hosted by rock-forming minerals. Phosphate, from the breakdown of apatite, and REEs form monazite in the laterite.

Fig. 2. Chondrite-normalized rare earth element diagram for laterite and carbonatite samples from the Mount Weld deposit.

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