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Review

Potential Future Alternative Resources for Rare Earth Elements:

Opportunities and Challenges
Balaram Vysetti

CSIR - National Geophysical Research Institute, Hyderabad – 500 007, India

* Correspondence: [email protected]

Abstract: Currently, there is increasing industrial demand for rare earth elements (REE) as these
elements are now integral to the manufacture of many carbon-neutral technologies. The depleting
REE ores and increasing mining costs are prompting to look for alternative sources for these valua-
ble metals, particularly from waste streams. Although REE concentrations in most of the alternate
resources are lower than current REE ores, some sources such as marine sediments, coal ash, and
industrial wastes like red mud are looking promising with significant concentrations of REE in
them. This review focuses on the alternative resources for REE such as ocean bottom sediments,
continental shelf sediments, river sediments, stream sediments, lake sediments, phosphorites de-
posits, industrial waste products like red mud, and phosphogypsum, coal, coal fly ash, and related
materials, waste rock sources from old and closed mines, acid mine drainage, and recycling of e-
waste. Possible future Moon exploration and mining for REE and other valuable minerals are also
discussed. It is evident that REE extractions from both primary and secondary ores alone are not
adequate to meet the current demand, and sustainable REE recovery from the alternative resources
described here is also necessary to meet the growing REE demand. An attempt is made to identify
the potential of these alternative resources and sustainability challenges, benefits, and possible en-
vironmental hazards to meet the growing challenges in meeting the future REE requirements.

Keywords: rare earth elements; deposits; alternative sources; marine sediments; river sediments;
phosphorites; red mud; fly ash; acid mine drainage; e-waste; extra-terrestrial

1. Introduction
Seventeen elements in the periodic table including fifteen lanthanides (La, Ce, Pr, Nd,
Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) plus Sc, and Y are often collectively
referred to as rare earth elements (REE). In nature, REE do not occur as single native met-
als, such as gold or silver, instead because of their similar physical and chemical properties
very often they occur together in several geologic formations in many ores or minerals as
minor or major constituents. Due to their unique physical, chemical, mechanical, elec-
tronic, magnetic, luminescent, phosphorescent, and catalytic properties, these elements
have become exceptionally important during the last couple of decades, and there has
been an explosion in the industrial application of these elements in different high technol-
ogy devices such as smartphones, computers, televisions, light emitting diodes, catalysts
for fuel cells, corrosion inhibitors, hard drives, and magnets for wind turbines and other
power generating systems. They are also crucial for national security as they are exten-
sively used in several military defence systems [1-3]. Their important medical applications
include metallic implants, lasers, and magnetic resonance imaging (MRI) measurements
[4]. REE are vital even to the space industry as they are used in everything from launch
vehicles to national defence and commercial communications and observation satellites.
REE are also used in making catalysts in several industrial processes as well as in the fab-
rication of autocatalytic catalytic converters in transport vehicles [5,6]. Although REE de-
posits are found practically in all parts of the world, currently there is a global shortage,
due to the decreasing number of economically profitable deposits. Also, our reliance on

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REE in our high-tech gadget-hungry world is growing with time, but their supply is far
from secure. Unfortunately, the conventional ore resources are becoming depleted, as the
demand for REE increases, and the industry is paying attention to unconventional re-
sources like coal, recycling, and marine sediments as alternative sources for these ele-
ments. It is also very important to maintain a proper supply chain to meet the demand for
the development of highly advanced technologies. Even the substitution of REE by other
cheaper metals is difficult for most applications, though powerful permanent magnets
made out of iron and nitrogen (iron nitride, Fe16N2) are helping the automotive and wind
energy industries in a small way [7]. Pavel et al. [8] studied the possibilities of substitution
of REE in wind turbines in order to reduce the dependency on REE, but later it was found
that these claims were impossible without neodymium. As a result, recycling is being
scaled up in several countries at present. Many approaches such as physical, chemical,
and biological procedures such as pyrometallurgy, solvent extraction, and membrane sep-
aration are available for the efficient extraction of REE from these resources [9]. One very
important aspect is that currently extracted ore grades, with an average of 5% REE and
running as high as 15%, have far higher concentrations than most of the discussed alter-
native sources [10]. Since only a few countries are producing these elements on a commer-
cial scale, meeting the growing demand for these elements is becoming exceedingly diffi-
cult in several other countries. As the demand for REE is growing and the conventional
ores are also getting depleted, attention is turning to unconventional and alternative REE
resources. Therefore, it is very important to understand the global REE resources includ-
ing alternative resources, and their production scenario and take measures against future
prospects. Therefore, this study which is the first of its kind brings out a summary of the
primary, and secondary, REE deposits, and a comprehensive report on alternative REE
resources and their potential to meet the current and future demand. This article also
serves as technical information for alternative resources for REE other than the primary
and secondary resources to policymakers and other stakeholders who are concerned. Be-
fore knowing more about alternative REE resources, a short review of the major REE pri-
mary and secondary deposits is presented below:

2. REE Deposits
Although REE comprise significant amounts of a wide range of minerals including
oxides, silicates, carbonates, phosphates, and halides, almost all production comes from
less than ten minerals such as apatite, monazite, xenotime, allanite, and bastnasite [11].
Currently, these deposits are mainly located in China, Brazil, Vietnam, Russia, and India.
Though China has been dominating in this area, several other countries such as the USA,
Australia, Turkey and Sweden have successfully discovered new REE deposits recently.
REE deposits are divided into primary (formed by magmatic, hydrothermal and/or met-
amorphic processes) and secondary deposits (formed by weathering and sedimentary
transport) depending on their form of occurrence, genetic associations, and mineralogy
[12]. Figure 1 Illustrative view of different types of REE resources including the potential
alternate future resources [13]

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Figure 1. Illustrative view of different types of REE resources including the potential alternate future
resources in light shaded, modified after [13].

2.1. Primary Deposits

Primary deposits of REE are commonly associated with carbonatites and alkaline ig-
neous rocks, pegmatites, iron oxide copper-gold deposits, and vein and skarn deposits.
Of these carbonatites and peralkaline silicate rocks with appreciable concentrations of
REE are the most important REE resources [13, 14]. These REE deposits in igneous rocks
have played an important role in meeting the industrial demand for decades. These igne-
ous mineral deposits can be divided into five distinct categories depending on the prove-
nance, the evolution of the magma, and the rock types hosting mineralization: i) carbon-
atites, ii) peralkaline silica undersaturated rocks, iii) peralkaline granites and pegmatites,
iv) pegmatites associated with sub- to metaluminous granites, and v) Fe oxide–phosphate
deposits [15]. More insights on these primary REE deposits were presented by Weng et al.
[16] and Dushyantha et al. [12]. Skarn deposits of REE are important in sustainable eco-
nomic development across the world [17]. In Fe oxide–phosphate deposits, these elements
are concentrated in apatite minerals [18].

2.2. Secondary Deposits

Some of the important secondary deposits of REE are laterites, ion adsorption clays,
and placer deposits. Ion-adsorption deposits, which are formed due to the erosion and
weathering of primary deposits from within weathering crusts which supply more than
95% of the global HREE demand. Intensive lateritic weathering of bedrocks under tropical
or sub-tropical climatic conditions can form a variety of secondary deposits which may
range in composition from aluminous bauxites to iron and niobium, and REE [19]. Re-
cently Jo and Shin [20] reported REE-enriched weathered anorthosite rocks with ΣREE
range 242 – 857 µg/g. Ionic clays, formed by the natural weathering process of REE-min-
erals and the adsorption of the resulting liberated REE ions onto the clay surface, are an
important resource for critical REE. These ion-adsorption clay deposits are most suitable
for in situ leaching mining, and supply > 95% of the global HREE demand [21]. Ion-ad-
sorption REE deposits are mostly developed due to weathering of REE-rich granites and
REE ions are mainly adsorbed on clay minerals [22]. Currently, regolith-hosted REE de-
posits from areas with abundant REE deposits have become one of the major sources of
global REE. Regolith-hosted deposits with abundant REE around Meizhou City, Guang-
dong Province, South China with the highest ΣREE of 1162 µg/g were reported recently
by Lin et al. [23]. The REE concentrations in the regolith-hosted REE deposits in Chilean
coastal range of the central Andes were found to be up to 2000 µg/g [24]. Beach sands are
the products of a combination of weathering, fragmentation and degradation and are
well-known for their economic concentration of heavy minerals like monazite, illuminate,
zircon, rutile, allanite, sillimanite and garnet. REE are abundant in some of these minerals,
particularly in monazite and allanite [25]. Black shales can also be considered as secondary
resource for these valuable metals. Recently, El-Anwar et al. [26] reported REE enrichment
(average 255.3–325.3 µg/g) in black shales of the Safaga-Qussier sector, Egypt. Another

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such study is reported from the rock-soil-moss system in the black shale area in China
with an average concentration of ∑REE around 245 µg/g [27]. These recent studies to-
gether with the industry standard of ~ 300 µg/g cut-off grade for mining, prompt more
studies on black shale formations worldwide before considering the black shale deposits
as a source of REE. Ketris and Yudovich [28] reported an average worldwide REE concen-
tration of 134.19 in black shales. Geothermal fluids are potentially significant sources of
valuable minerals and metals. The total REE in geothermal waters in places like Iceland
can go up to 21.76 µg/g [29]. Kurzawa et al. [30] in an attempt to understand the REE
concentrations in the mineral and thermal waters in the Polish Lowlands, found that high
temperature (T > 60 °C) favoured the release of the more easily soluble REE from rocks
into the water. Wei et al. [31] recently reported the total REE content of the geothermal
water in the range of 0.059‒0.547 ng/ml, in the Ganzi–Litang fault, western Sichuan, China.
The REE contents in geothermal waters are related to the reservoir lithology and are sig-
nificantly influenced by pH and HCO3−, Na+, and Mn minerals. Though the REE content
in geothermal waters is not considerable, if the abundant geothermal waters in places such
as Iceland are taken into consideration, this source could be one of the most promising
ones for REE with an efficient extraction technology. Li et al. [32] reported moderately
high concentrations of REE ranging from105 to 195 µg/g at an average concentration of
151µg/g in oil shale samples in Tongchuan City, Southern Ordos Basin, China prompting
the necessity for further investigations to understand the REE potential of these rocks.

2.3. Different Types Potential Alternative Deposits

So far, the identified primary and secondary REE resources are not able to meet the
global demand and requirements. Finding out and establishing alternative resources for
REE has been a topic of high interest for the past decade. Hence, lot of studies are going
on for the identification of the potential alternative deposits to meet the growing demand
world over. Powerful analytical techniques such as inductively coupled plasma mass
spectroscopy (ICP-MS), inductively coupled plasma optical emission spectrometry (ICP-
AES), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-
EDX), x-ray fluorescence spectrometry (XRF), x-ray diffractometry (XRD), laser induced
breakdown spectroscopy (LIBS), and TESCAN, integrated mineral analysis (TIMA), are
being utilised to understand the future potential of various alternative REE resources [33-
36]. Following are some of the most important alternative sources for REE.

2.3.1. Ocean Bottom Sediments, and Continental Shelf Sediments

Rifting of the continents has formed widespread sedimentary basins as rifting pro-
cesses produce greater subsidence and lower basal heat flow, enlarging the depth extent
of hydrothermal circulation and favouring the formation of giant deposits of elements
such as copper, lead, zinc and nickel [37]. Several studies in recent times revealed that
marine sediments such as ferromanganese crusts (cobalt crusts), manganese nodules, and
marine mud from different parts of deep oceans are found to contain significant concen-
trations of REE and Y [38-41]. REE concentration ranges (µg/g) in some marine sediments
from different oceans across the globe are presented in Table 1. Recent studies suggested
that the continental shelf sediments of the Atlantic Ocean and Northern South China could
potentially become resources for REE, similar to metalliferous deep-sea sediments [42,43].
Sediment samples from the northern South China Sea continental shelf reported concen-
trations of REE ranging from 32.97 µg/g to 349.07 µg/g, with an average concentration of
192.94 µg/g. These elevated concentrations of REE in the bottom sediments of Siberian
seas in the Arctic were found to be mainly controlled by the characteristics of the original
rocks [44]. Thus, deep-sea sediments because of their vast amounts of REE and a remark-
ably high proportion of HREE have attracted interest as a future REE resource. However,
at the moment the regulatory authorities are not able to take decisions on future seabed
mining because of the possible environmental effects of seabed mining [45].

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Table 1. Overview of REE range (µg/g) in marine sediments from different oceans (modified after
Balaram, 2019).

Ocean. Matrix REE range (µg/g) Reference

East Siberian Arctic Shelf Bottom sediments 104 to 220  [44]
Central North Pacific Ocean Siliceous sediments 810.4 [46]
Afanasy Niktin Seamount (ANS) in the
Cobalt crust 1727 – 2511 [38,39]
Eastern Equatorial Indian Ocean.
Mid-Pacific seamount Cobalt-rich crusts 2085 [47]
Indian Ocean Ferromanganese crust 928 - 1570 [48]
Scotia Sea Ferromanganese crust 3400 [49]
Eastern South Pacific Deep sea mud 1000 – 2230
North Pacific (east & west of Hawaiian [50]
Deep sea mud 400 – 1000
Islands)
Minamitorishima Island in the West-
REE-Rich Mud >1446.2 (REE+Y) [51]
ern North Pacific
Ferromanganese nodule
South China Sea 1460 (avg) [52]
deposits
REY-rich mud > 400
Indian Ocean [53]
Marine sediments 585 - 920
Ferromanganese crust,
summit of southern 1139
seamount
Andaman Sea, Indian Ocean [54]
Ferromanganese crust
within the two peaks of 2285
the same seamount.
Lakshadweep Sea, Indian Ocean Ferromanganese crust, La (200) & Y (150) [55]
West Sewell Ridge, Andaman Sea, In- Ferromanganese crust 1600
[56]
dian Ocean Manganese nodules 1186
Clarion-Clipperton Fracture Zone,
Deep-sea sediments >700 [57]
North-eastern Pacific Ocean
West Clarion–Clipperton Zone, Pacific
Marine sediments 454.7 (REE+Y) [58]
Ocean
North Pacific Ocean near
Deep-sea mud > 5,000 (REE+Y) [60]
Minamitorishima Island, Japan
Mid Pacific Ocean Fe-Mn nodules 1178 - 1434 [60]
Deep nodules 1326
Pacific Ocean [61]
Shallow nodules 1398
Pacific Ocean ocean-floor sediments 22,000 [62]

2.3.2. Phosphorites and Related Deposits

Phosphate ores are divided into two main types on the basis of their origin: sedimen-
tary and igneous phosphate rocks, about 80 % of which are derived from marine origin,
and around 17 % are derived from igneous rocks, and the remaining deposits come from
the residual sedimentary and guano-type deposits [63]. These rocks contain up to 1%
∑REE, and phosphate rock ores both igneous and sedimentary are, therefore, potential
future resources of REE. Igneous phosphate rocks (e.g., Kola Peninsula, Russia, and Bra-
zil), and sedimentary phosphate rocks which are formed by the deposition of phosphate-
rich materials in marine environments and are also known as phosphorites are found in
Florida, US, Morocco, and the Middle East [64]. Marine phosphorites concentrate REE in-
cluding Y during the early diagenetic process. The REE content in seamount phosphorites
is far greater than in continental margin phosphorites [39]. Morocco has the largest phos-
phate ore reserves in the world with 50 billion tons, followed by China and Egypt with
3.2 and 2.8 billion tons of phosphate ores respectively [65]. Based on the REE concentration
data presented in Table 2. phosphorite deposits can be considered promising and could
represent a profitable alternative source for REE in the future. Buccione et al. [66] made

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an attempt for understanding the economic potential of Northern African phosphorite

deposits as alternative REE resources. The very high concentrations of REE (up to 1759
µg/g) in the Northern African phosphorites revealed that they can be considered promis-
ing alternative REE resources.

Table 2. Concentrations of REE in marine phosphorites and related rocks from different regions
across the world.

Average Concentration
Ocean Phosphorites Reference
(µg/g)
Seamount phos-
727 (∑REE+ Y)
phorites
Pacific and northeast Atlantic [40]
Continental mar-
161 (∑REE+ Y)
gin phosphorites
Danzhai phospho-
Doushantou Formation, South China 21 to 447 (∑REE) [67]
rite deposit
Meishucun excavation sites, South Cambrian phos-
99.1 - 709.7 (∑REE) [68]
China phorites
Sedimentary Abu Tartur phosphate
Phosphate ore 0.05-0.20 wt. % (∑REE) [65]
ore, Egypt
Mississippian phosphorites, USA Phosphorite ore 18,000 (∑REE) [69]
Mountain
Phosphorite ore
Pass phosphorites, USA
Chinese clay-type Phosphorite de-
Phosphorite ore 500 to 2000 (∑REE) [70]
posits
Hazm Al-Jalamis Phosphorites,
Phosphorites <121.8 (∑REE+ Y) [71]
Saudi Arabia
Pabdeh Formation, Khormuj anti-
Phosphorites 48 to 682 ∑REE [72]
cline, SW of Iran
Northern African phosphorite de-
posits (Morocco, Algeria and Tuni- 39.2 to 1759.4 ∑REE [66]
sia)
Phosphorus-bear-
ing 330 ∑REY
dolomites
South China [73]
Phosphorus dolo-
676 ∑REY
mites
Phosphorites 1477 ∑REY

2.3.3. Stream Sediments, River Sediments and Lake Sediments

If REE-bearing source rocks are present in the catchment area of a river or a lake or a
stream, the corresponding sediments continuously accumulate transported material and
get enriched with respect to REE due to the physical and chemical weathering and erosion
of source rocks. An increasing trend in the concentration of REE is seen in the sediments
starting from river sediments to the estuary and adjacent bay in the case of Yellow River
(Table 3). In sediments, Fe minerals and clay minerals usually promote the accumulation
of REE. Recently, Klein et al. [74] undertook a study of the occurrence and spatial distri-
bution of REE along with a few other elements such as Ga, Ge, Nb, In, Te, and Ta in the
Rhine River sediments and its tributaries in Europe. The Rhine River represents one of the
most important waterways in Europe accommodating a large number of industries with
a catchment area of around 60 million inhabitants. The ∑REE concentrations show a
steady increase along the Rhine River (Table 3) inferring that. the sources for these ele-
ments could be from natural as well as anthropogenic activities as the river sediments
pose an important sink for anthropogenically introduced REE. Ramesh et al. [75] pre-
sented the distribution pattern of REE and several other trace elements in the sediments
of the Himalayan rivers (Table 3). Since this data is more than two decades, the current

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concentrations can be considerably higher due to increased anthropogenic inputs as well

as natural inputs. The Lake sediments in Sri Lanka recorded 1101 µg/g of REE (Table 3)
because it is in the proximity of the Eppawala phosphate deposit [76]. Either REE contain-
ing source rocks or anthropogenic inputs, or both can be contribute for REE in all these
sediments.

Table 3. REE concentrations in stream sediments, river sediments, and lake sediments in different
parts of the world.

Country Type of sediment ∑REE Reference

Indigirka River, in the Laptev Sea River sediments 124 to 197 [44]
Upper Rhine 136.07
Middle Rhine 215.32
Rhine river sediments, Europe [74]
Lower Rhine 340.45
Tributaries 291.39
Brahmaputra 95
Ganges 97
Megna 107
Himalayan river system sediments [75]
Padma 131
Jamuna 152
Yamuna 100
Cauvery 171
Pennar 203
Krishna 131
Rivers of the east coast of India Godavari-Vasista 194 [77]
Godavari-Gauthami 290
Mahanadi 270
Hooghly 167
South America Amazon sediments 217 [78]
The Mgoua watershed, Cameroon, Af- 282 to 728
Sediments [79]
rica Average 550
Stream sediments 212
China Catchment sediments 187 [80]
Soils 190
Sri Lanka Lake sediments* 1011 [74]
River sediment 149
Yellow River, China Estuary 165 [81]
Laizhou Bay 173
* Lake sediments in the proximity of the Eppawala phosphate deposit in Sri Lanka. Sediment frac-
tion (<63 µm) of each sample.

2.3.4. Coal, Coal Fly Ash and Related Materials

Coal contains trace amounts of REE either in the form of discrete minerals or chemi-
cally bound to organic matter. Several investigations have demonstrated that coal ash may
represent a promising alternative resource of REE as the demand for these metals is in-
creasing. Some investigations revealed that the total REE concentrations in the organic
and inorganic phases are 31 µg/g and 1,141 µg/g, respectively [82]. Coal fly ash is one of
the largest industrial waste streams in the world which contains significant concentrations
of REE and has the potential to become an important alternative resource for REE. Until
now, this is being used as a building material for construction, concrete and road base,
ceramics, etc. A of studies are going on the development of economically feasible proce-
dures for the extraction of REE from coal and coal fly ash as there are large global reserves
of coal and coal fly ash the world over. Yesenchak et al. [83] made a study of West Virgin-
ia's coal deposits for understanding their economic potential on an ash basis with respect
to REE and also to gain insight into elemental modes of occurrence and possible enrich-
ment mechanisms of these elements. Dai et al. [84] have provided an excellent review of

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anomalous REE and yttrium concentrations in coal. Table 4 presents the potential of these
alternative REE resources. A big country like China uses about 4 billion tons of coal for its
power plants to generate electricity which produces about 500–550 million tons of fly ash
[85]. Coal and coal combustion products such as fly ash, bottom ash, and incinerator ash
are found to contain significant amounts of REE as most coal samples contain minor
amounts of rhabdophane, Nd, Ce, La (PO4).H2O, monazite, (Ce, La, Th, Nd)PO4, and xe-
notime (Y, Er)PO4 [86]. Some of the coal resources are enriched in REE due to the contri-
butions from both detrital and hydrothermal sources (Hower et al. [87]. Significant con-
centrations of REE found in the global reserves of coal (average REE concentrations are
estimated at 380–470 µg/g) and its by-products have prompted numerous research studies
to understand their economic feasibility as alternative resources for REE and led to the
development of several efficient procedures to extract REE from coal ashes [88]. Hence,
coal fly ash is considered a potential alternative source for REE in recent years. Recently
Lu et al. [89] reported that the REE and Y contents of coals from southwestern China are
high, and the coal reserves and their by-products are suitable as potential REE sources.
For example, in Poland which is the second biggest coal consumer in the European Union,
there can be huge reserves of fly ash which is rich in REE. The concentrations of REE in
certain coal deposits such as Pond Creek coalbed, Pike County, Kentucky, US can go up
to 1000 µg/g or more. The collection and chemical analysis of over 4,000 samples including
acid mine drainage, coal, and coal ash samples, with REE concentrations ranging from
ng/ml for raw acid mine drainage materials to thousands of ppm (µg/g) for alternative
coal-based resources such as coal and coal fly ash, USGS [90] recently demonstrated the
technical feasibility of producing high-purity critical minerals, including REE, from low-
grade coal-based materials. For a thorough understanding of the origin of anomalous con-
centrations of REE in coal, in addition to the influence of diagenetic processes such as
temperature, pressure, and time associated with coal-rank advance, it is also necessary to
understand a few more interaction mechanisms such as the influence of marine environ-
ments, input of hydrothermal fluids, volcanic ashes, and natural waters on peat swamp
[83]. In addition, the presence of considerable amounts of radioactive nuclides (226Ra, 232Th,
40K and 238U) in fly ash must be also considered while developing efficient procedures for

the extraction of REE, and see that these hazardous radionuclides should not escape in to
the environment causing radioactive pollution in the surrounding [91,92].

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Table 4. Concentrations of rare earth elements in coal, and coal fly ash from different sources around
the world.

Place & Country Material ∑REE (µg/g) Reference

450 [93]
World average Fly ash
404 [84]
Poland Fly ash 101 - 543 [94]
Faer power plant in Guizhou
Fly ash 240.20 to 520.27 [95]
Province, China
lignite coal-based thermal
Fly ash 2100 [96]
power plants, India
Collie Basin, Western Aus-
Fly ash 0.21% ∑REO [35]
tralia
Pond Creek coalbed, Pike
Coal <300 to >1000 [87]
County, Kentucky, US
World hard coal 69
World low-rank coal 65
World coal Coal 68 [84]
US coal 62
China 138
South Korea Fly ash 267 to 556 [97]
Coal bed, Eastern Kentucky,
Fire clay 1965–4198 [98]
US
Qianxi coal-fired power plant,
Fly ash 630.51 [73]
Guizhou province, China
Thermal Power Station II (TS
II) of Neyveli Lignite Corpora- 2160 (∑REE)
Fly ash [99]
tion (NLC), Chennai, Tamil 300 (Y)
Nadu, India
WV MKT
297
underclay
WV MKT
coarse coal 345
Central Appalachian Coal-Re-
refuse
lated Strata, West Virginia
Central PA [100]
(WV) and Central Pennsylva-
LKT under- 221
nia (PA), US
clay
Central PA
MKT under- 728
clay

2.3.5. Industrial by Waste Products Like Red Mud, and Phosphogypsum

Industrial by-products like low-grade bauxite, red mud, phosphogypsum, gem min-
ing waste, and slags are found to contain substantial amounts of REE and are hence these
are also considered alternative resources for REE. In fact, mining waste in many cases
contain high concentrations of toxic substances and is considered a threat to the environ-
ment. However, mining waste discharges produced at the bauxite, phosphate rock and
other ore mines may also become valuable resources, especially for REE. For example, in
the process of refining titanium dioxide from the mineral ilmenite, REE oxides are pro-
duced as co-products. Another example is, during the leaching of bauxite by NaOH by
the Bayer process for alumina production, a solid waste known as red mud is generated
which contains substantial amounts of REE (Table 5). More than a decade back, the global
annual generation of bauxite residue was around 120 million tonnes and 2.7 billion tonnes
of this material was stockpiled by then [101]. According to Swain et al. [102], the global
production of bauxite and red mud during 2010-19 is 2999 and 1518 million tons respec-
tively. China, Australia, Brazil, India, the US, and Russia produce bauxite waste (red mud)

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in large quantities. Since the Bayer processes inception, large amounts of red mud are
getting stockpiled, and with the increasing awareness of the availability of huge concen-
trations of REE in this industrial waste material, this would soon become an important
alternative resource for REE [103]. Both igneous and sedimentary phosphate rock deposits
are used for manufacturing fertilizers. Recent studies revealed that low–grade saprolite
ore which is primarily exploited for its gold and copper, also contains significant amounts
of REE [104]. The vast amount of gem mining industry tailings of past and present mining
activities in Sri Lanka was proven to contain up to 0.3% REE which can become a potential
secondary source for many critical raw materials, including REE [105]. Initially, people
used red mud to make bricks, and in cement production, but its potential to be an alter-
native resource for REE has been recently realised. During the production of wet phos-
phoric acid and phosphate fertilizer from phosphate ores, a solid phosphogypsum by-
product is produced to which most of the REE (>80%) in the phosphate ore are transferred
[65]. Phosphogypsum can show low levels of radioactivity because of the presence of
small amounts of uranium and thorium, but also useful as a valuable REE resource (Table
6). In many instances, industrial metallurgical waste dumps are contaminated with heavy
metals posing a huge threat to both humans and the ecosystem. Phosphogypsum
(CaSO4·2H2O) which is rich in REE is a waste generated during the production of the phos-
phoric acid process and the composition of impurities depends on the source of the phos-
phate. Phosphogypsum and uranium tailings are being used to extract REE in Poland
[106]. Such industrial metal wastes can become sources for the extraction of REE. Baron
[107] found significant amounts of valuable REE (Table 6) from such waste material in
Poland. For example, Arctic Loparite ore tailings in the Kola Peninsula, North-western
Russia are being effectively used to extract REE using bioleaching methods [131].

Table 5. REE concentrations (µg/g) of red mud from different countries in comparison with earth
average crust composition, modified from [103].

REE (µg/g)
Location
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Yb Y Sc
Average in Earth’s crust [108] 39 66 9 41 7 - 6 1 5 1 3 3 33 22
Chinalco, China [109] 416 842 95 341 64 - 56 184 48 25 28 28 266 158
Australia [110] - - - - - - - - - - - - 68 54
Brazil [111] - - - - - - - - - - - - 24 43
India [112] 110 70 0.5 - - - - - - - - - 1 5
India [113] 58 98 - - - - - - - - - - - 48
India [109] 112 191 18 48 9 - 7 - 4 - 1 2 13 58
Jamaica [114] 287 366 74 69 0 - 37 0 37 5 21 16 373 55
Greece [115] 114 386 28 98 21 - 22 - 16 4 13 4 75 121
Alumine de Greece, Greece [116] 130 480 29 107 19 - 22 3 20 4 13 13 108 -
Greece [117] 127 409 28 103 20 - 18 2 19 3 11 13 98 -
Greece [118] 149 418 26 115 29 5.0 23 - 1 4.3. 17 16 91.
Ajka, Hungary [119] 114 368 - - - - - - - - - - 68 -
Turkey [117] 169 480 47 161 32 - 4 26 23 4 13 14 113 -
Russian Federation [120] - - - - - - - - - - - - 53 25
Russian Federation [109] - - - - - - - - - - - - - 90
Iran [120] - - - - - - - - - - - - 1 19

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Table 6. Concentrations of REE in mine tailings and mine waste of different mines, industrial mate-
rials, and industrial waste.

Country Industrial waste ∑REE Reference

Uranium mine tailings, Sudety
Poland 64.9- 109.8 µg/g [106]
region
Southern Shanxi
Low-grade bauxite 1539 µg/g [121]
Province, China
192 to 1109 (avg. 463)
Greece Bauxite [122]
ΣREE + Y+Sc
1.14%
Australia Low–grade saprolite ore [104]
(∑REE oxides)
Poland Metallurgical industry waste. >140 µg/g [107]
Water Leach Purification (WLP) 88367 µg/g with Gd as the
Malaysia [123]
residue most abundant element
Canada Red Mud 0.03 wt% [124]
Jamaica Red Mud >1303 (REE+Y+Sc) [114]
Alumine de Greece,
Red Mud >948 (REE+Y) [116]
Greece
Turkey Red Mud > 1086 (REE+Y) [117]
Sri Lanka Gem Mine 0.3% (∑REE oxides) [105]
Bagre-Nechí mining Mine waste (mostly gold mine
2.19% (Ce, La, Nd & Pr) [125]
district, Colombia residue and monazite waste)
Russia Different types of red mud Sc (> 100 µg/g) [126]
Greece Bauxite residue (Red mud) 0.1% (∑REE+Y+Sc) [115]
Agios Nikolaos,
Bauxite residue ∑REE 260 & Sc 120 [127]
Greece
Mineral formations (TMF) from
SARECO LLP, Ka-
the processing of phosphate ura- 5% [127]
zakhstan
nium ores
Russia Phosphogypsum 0.43 - 0.52% [129]
Philippine Phosphogypsum 266 µg/g [130]

2.3.6. Waste Rock Sources From Old and Closed Mines

Over 100 billion tonnes of solid waste are produced annually through mining opera-
tions the world over. The use of mine waste and mine tailings is attractive as this will
reduce mining costs because the material is already excavated from the mines which
would make it easier to access the minerals.
Recently Abaka-Wood et al. [132] provided a review highlighting the application of
the new knowledge for the enhanced REE minerals recovery from selected iron-oxide-
silicate-rich tailings and other alternative resources of similar mineralogical composition.

2.3.7. Acid Mine Drainage

Acid mine drainage (AMD) of certain industrial effluents such as coal, REE, and ura-
nium mines, is also considered a potential source of REE though the concentration of
∑REE will be in the ng/ml range in the raw acid mine drainage samples. Table 7 presents
concentrations of REE in AMD from different mines across the globe. This is a potential
alternative REE resource and the recovery of REE remains largely unexplored though a
lot of efficient extraction procedures are being developed. Acid mine drainage is produced
by the oxidation of metallic sulphides present in some ores and tailings because of the
instability of sulphides, which leads to the generation of sulfuric acid that promotes the
leaching of the metals that make up these materials. Depending on the deposit type, acid
waters can contain REE in significant concentrations. For example, the acid effluent of a
closed uranium mine in Brazil contains 130 µg/ml REE. This acid effluent is treated with
lime to produce a precipitate containing 7 % of REE [133], though there are other methods
like ion exchange, solvent extraction, and co-precipitation for their recovery. The

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treatment of acid mine drainage is often carried out by neutralization, oxidation, and
metal hydroxide precipitation. The precipitates obtained after the treatment of the North-
ern Appalachian Coal Basin in the US, the REE concentrations of the precipitates varied
from 29 to 1286 µg/g with an average of 517 µg/g [134, 135]. Since REE are present in low
concentrations in mining wastewaters and acid mine drainage, adsorbents such as cellu-
losic materials and ion exchange materials could be more useful as part of extraction/pre-
concentration and/or purification processes. Pyrgaki et al. [136] in a recent review de-
scribed mining waste and mine water as promising sources of REE if their extraction is
coupled with the simultaneous removal of toxic pollutants. These authors reported very
high concentrations of ∑REE+Y of 77 to 1957.7 µg/g in coal combustion ashes, bauxite
residue and phosphogypsum, and 1.6 to 24.8 µg/ml in mine discharges from different coal
and ore mining areas around the globe

Table 7. Concentrations of REE in acid mine drainage (AMD) from different mines across the globe.

Concentration of
Name and location of the mine Type Reference
∑REE
Minas Gerais, Brazil AMD 130 ng/ml [133]
Staszic post-mining, Poland Uranium mine 993.3 µg/ml [106]
Coal mine 282 ng/ml
Treated precipitate 517 µg/g
Northern and Central Appalachian Coal Basins, US [134,135]
Coal mine, Treated
724 µg/g
AMD
Pregnant leach solu- 132.02 µg/g
Central Appalachian AMD source, US [137]
tion ∑REE+Y+Sc
<221.8 ng/ml
Sao Domingo mining complex, Iberian Pyrite Belt, Portugal AMD [138]

Xingren coalfield, China AMD 118 to 926 ng/ml [139]

2.3.7. Recycling of E-Waste such as Magnets, etc.

As the primary and secondary REE ores are getting depleted, alternative sources such
as the recycling of e-waste for a substantial recovery of REE gained prominence in recent
times [140]. Our dependence on REE for the electronic gadgets required for our daily life
and green technologies is increasing, but the required supply of these elements is far from
secure. Because of the environmental problems and the escalating cost of mining, the focus
is now shifting toward recycling. Recycling REE to some extent can meet this demand.
Recycling electronic wastes such as magnets, nickel-metal hydride batteries, hard discs
from laptops, desktop computers, mobile phones, loudspeakers, scrap alloy, spent cata-
lysts, and waste light-emitting diodes (LEDs) currently end up in landfills. Instead, these
electronic devices can be used to recover REE as a mixture of their oxides which later can
be reduced to the production of new magnets. More than 50 million tons of e-waste is
generated globally every year [141]. Many economically important metals like REE, Cu,
Co, Li, Sn, Ta, Ga, Au, and Ag can be recovered from this kind of electronic waste without
affecting the environment [142]. The REE recovery from waste helps sustainable develop-
ment through the circular economy. Particularly five elements, namely Nd, Eu, Tb, Dy,
and Y are extremely important and their demand is expected to grow by 30% in the com-
ing decade. For example, recycling of scrap Nd-Fe-B magnets usually provide substantial
amounts of Nd, Pr, Dy, and sometimes Tb. Unfortunately, the recycling activity is not
going on in a big way at present mainly because the e-waste contains a very less quantity
of these metals. For example, each smartphone contains just 50 mg Nd and 10 mg Pr (Table
8), and in touch screen devices, some of these metals are distributed throughout the ma-
terial at the molecular scale, though items like wind turbines contain substantial amounts
of REE. On the other hand, huge quantities of REE are required for manufacturing certain
items such as navy ships, defence aircraft, and permanent magnets. One of the major ob-
stacles in recycling the REE is, the complexity of usages of these elements in a variety of

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applications with amounts ranging from a few milligrams to a few kilograms [143]. An-
other critical factor that is affecting the recycling activity of the REE is the lack of cost-
effective methods for their extraction from e-waste both collectively and individually.
Hence, the efficient recovery of these metals becomes entirely difficult and not cost-effec-
tive and as a result, until recently only less than 1% e-waste has been recycled for REE
[144]. But nevertheless, both the US and Japan have intensified their research studies on
recycling as the dependence on REE is comparatively high in these countries. Rizos et al.
[145] reviewed the recycling of REE permanent magnets from end-of-life (EoL) products
and opined that if systematically implemented, this could be among the main avenues for
meeting the EU’s future REE needs and for mitigating supply risks.

Table 8. Amounts of rare earth elements in different e-waste items.

E-waste item REE Concentration per Unit Reference

9Nickel metal hydride (NiMH) battery ∑REE 5–25% [146]
Cathode-ray tube (CRT) phosphor (as a
∑REE 1–7 g [147]
coating on the panel.
Fluorescent lamp ∑REE + Y 301.2 mg/1 g powder
[148]
Cathode-ray tube (CRT) 265 mg/1 g powder
Navy submarines ∑REE 3636 kg
Navy surface ships ∑REE 1818 kg
Lockheed-Martin F-35 ∑REE 416 kg
[144]
Toyota Prius ∑REE 15 kg
Air conditioner ∑REE 120 g
Mobile phone ∑REE 0.5 g
Wind turbine that generates 3.5 MW Elec-
∑REE 600 Kg [3]
tricity
Fly and bottom ash ∑REE 0.9-1.3% [10]
SmCo5 magnet Sm 21.94% [149]
NdFeB magnet Nd & Pr 64.5% & 17.32% [150]

2.3.9. Extraterrestrial
The moon, Earth’s nearest neighbour in space has long been considered a desirable
location for space mining operations. Earlier studies have demonstrated that the Moon
contains vast amounts of natural resources, like uranium, titanium, silicon, water, nickel,
precious metals, REE, and 3He at much higher concentrations than those found on Earth
[151]. Robotic technologies will be extensively utilised for future mining on the moon to
achieve precise localization, and conceptual mapping of the lunar surface [152]. Conse-
quently, both government organisations from countries like the US and China, and private
sectors are engaged in future space mining activities [153]. Recently eight nations signed
a US-led Artemis Program for moon exploration and beyond. The path is now clear for
those eight nations — Australia, Canada, Japan, Luxembourg, Italy, the UK, the UAE, and
the U.S. — to participate in NASA's Artemis program of crewed lunar exploration which
aims to establish a sustainable human presence on and around the moon by the end of the
decade. In addition, several missions planned for the exploration of the Moon’s surface in
search of REE and other valuable minerals by countries such as the USA, China, India,
Japan, and Russia [154].

3. Conclusions and Future

Apart from other critical metals like Cu, Co, Ga, and Li, REE are also needed in big
quantities for the necessary transition from fossil fuels to green energy solutions for the
whole world to deliver net zero by 2050. Hence, there is a great need to intensify the ex-
ploration, mining, and extraction efforts for REE not only for the low-carbon energy tran-
sition but also for national security and consumer electronics applications. It is also time
for looking into alternative resources for REE as the primary and secondary REE resources

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are dwindling fast and it is becoming difficult for identifying new resources. In addition,
there is great uncertainty about the future REE supply from countries like China. The
work presented here indicates the range and variety of waste streams with significant REE
concentrations and with broader sustainability. Among the alternative resources de-
scribed here deep-sea sediments, coal fly ash, and industrial waste products such as red
mud and phosphogypsum are considered very promising. Future research will focus on
finding cheaper and greener ways of extracting REE from these alternative resources.
While developing efficient technologies for the extraction of REE from these alternate REE
resources, there is a great need to be careful about the possible emissions of toxic metals
like Cr, and Hg, radioactive metals like U, Th, and toxic organic compounds into the en-
vironment. Some recent studies have established the technical feasibility of a simple, eco-
nomic, and scalable process for the recovery of REE from most of these alternative REE
resources. Also, intense research is going on worldwide for the development of efficient
technologies for the recovery of REE from these alternative sources which is expected to
show a solution to the present global REE crisis. Some of the recent studies in this direction
also suggest that other issues such as environmental, economic, and social factors will
strongly influence the development of these alternative REE resources. There are also
many questions about the alternative sources to becoming real-world REE sources for
which plausible answers can be obtained only in the future.
Acknowledgement: The author would like to acknowledge the support of the Dr. Prakash Kumar,
Director, CSIR-National Geophysical Research Institute, Hyderabad, India.

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