Minerals Engineering 179 (2022) 107430

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

A review of environmental aspect of rare earth element extraction processes

and solution purification techniques
Deniz Talan, Qingqing Huang *
Department of Mining Engineering, West Virginia University, 365 Mineral Resources Building, 1374 Evansdale Drive, Morgantown, WV, United States

A R T I C L E I N F O A B S T R A C T

Keywords: Rare earth elements (REEs) are vital for the technology, military, and defense industries. They have been
Rare earth elements recognized as critical due to potential scarcity, supply constraints, and lack of minable concentrations. Therefore,
Thorium alternative sources are needed to meet the demand and continue manufacturing rare earth-dependent products.
Uranium
However, the environmental prospect of rare earth mining was not investigated enough, and comprehensive
Environmental impact
Separation
studies are lacking. It demands serious consideration as toxic radionuclides are seen in the same mineralization
Radioactivity as rare earths regardless of their primary or secondary sources. The concentration of these hazardous trace el­
ements may be elevated as a result of extraction and beneficiation processes. Unless proper separation and
disposal are performed, these radionuclides accumulate on the surface of the soil or integrate with aquatic
systems, which consequently raise environmental and health concerns. This review manuscript compiled the
environmental impact and aspect of rare earth extraction processes while addressing separation techniques for
these radioactive materials from rare earths, emphasizing selective precipitation, solvent extraction, and solid-
phase separation.

1. Introduction et al., 2015).

The formation of rare earths is diverse and complex. They do not
Rare earth elements or lanthanides refer to 15 elements with atomic occur as native elemental metals; instead, they are seen in various host
numbers from 57 to 71. Two other elements, scandium (Sc, atomic minerals, such as halides, carbonates, oxides, phosphates, and silicates
number 27) and yttrium (Y, atomic number 39) are also considered in (Rim et al., 2013; Suli et al., 2017). Due to the similarities in their ionic
the same group since they share similar chemical and physical proper­ radii, the rare earths can interchange with other minerals, making their
ties (Rim et al., 2013; Jorjani and Shahbazi, 2016; Anderson et al., 2017; concentration difficult (Yang, 2019). Besides, concentrated rare earth
Zhou et al., 2018). Contrary to their names, the abundance of rare earths deposits are limited, accounting for ineffective and uneconomical
in the earth’s crust is much higher than most other commodities (Jor­ extraction (Fouquet and Martel-Jantin, 2014; McLallan et al., 2014).
dens, 2016; Van Gosen et al., 2017). Even the least abundant thulium Although >200 rare earth-bearing minerals are being identified in na­
and lutetium have an average crystal abundance of approximately 200 ture, bastnaesite (REECO3F), monazite ((Th, REE)PO4), xenotime
times that of gold. As opposed to thulium and lutetium, cerium, yttrium, (REEPO4), and ion-adsorption clays are considered as the primary
lanthanum, and neodymium are the most abundant rare earths. On the sources due to their rare earth contents and economic feasibility.
basis of the atomic weight, rare earths are divided into two groups. The World resources are primarily constituted of bastnaesite and mona­
elements from lanthanum through gadolinium comprise the light rare zite deposits. Two of the world’s largest rare earth deposits, Mountain
earth elements (LREEs). In contrast, the rest and yttrium form heavy rare Pass (USA) and Bayan Obo (China), have bastnaesite as their rare earth
earths (HREEs), which are in higher demand because of their superior host mineral, which is particularly rich in light rare earths. Monazite is
strategic value (Van Gosen et al., 2019). Additionally, due to their generally seen in sediments and recovered, especially in coastal de­
importance in many industries and shortage in supply, neodymium posits. The deposits in Australia, Brazil, China, India, Malaysia, and
(Nd), terbium (Tb), yttrium (Y), dysprosium (Dy), and europium (Eu)) South Africa constitute the largest monazite deposits. Currently, it is
were classified as critical rare earth elements (CREEs) (Chu, 2011; Quinn extracted on the east coast of Brazil and India (Van Gosen et al., 2017).

* Corresponding author.
E-mail address: [email protected] (Q. Huang).

https://doi.org/10.1016/j.mineng.2022.107430
Received 11 June 2021; Received in revised form 22 January 2022; Accepted 28 January 2022
Available online 15 February 2022
0892-6875/© 2022 Elsevier Ltd. All rights reserved.
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Oppositely, xenotime contains a high concentration of heavy rare earths Table 2

and yttrium (Alex et al., 1998). Like xenotime, ion adsorption clays also Area of the use of rare earth elements (modified from Jyothi et al., 2020).
contain a considerable amount of heavy rare earths (typically 300 ppm). Rare Earth Elements Area of Use Category
They are different than the mineral-type (i.e., bastnaesite, monazite, and
Eu, Y Lighting Green Energy
xenotime) deposits and were discovered in granite weathering crust in La, Ce Batteries
Southern China in the late 60 s (Wang et al., 2018). Some of the most Nd, Pr, Dy Wind power
well-known and vital rare earth-bearing minerals are summarized in Nd, Pr, Sm, Dy, Tb Hybrid vehicles High-tech, daily life
Table 1. Y, Ce, Eu, Tb LCD screens devices
Nd, Gd Medical use (MRI)
Because of their unique magnetic, optical, and electrical properties, Nd, Pr, Ce, La Cell phones, CD and DVDs
rare earth elements have diverse industrial applications. As seen in Eu, Y, Tb Optics Defense
Table 2, the utilization areas of rare earth elements can be grouped into Dy, Tb Lasers
three: clean energy, defense, and high-tech and daily life devices (Jyothi Y, and others Aircraft materials
Nd, Pr, Sm, Dy, Tb Power and communication
et al., 2020). The military uses rare earths to produce night-vision
tools
goggles, communication, and GPS equipment. Likewise, these ele­ Nd, Y, La, Eu, and Solar transducers
ments are used in developing defense systems, such as jet engines, others
missile guidance systems, and satellites (Van Gosen et al., 2019). In
addition, they are heavily used to produce electronic devices such as
computers, cell phones, electric vehicle batteries, etc. Furthermore, source (i.e., coal, copper, pyrite, lead, zinc, gold mining, etc.), mine
lanthanum-based and cerium-based catalysts are commonly used in drainage also has considerable potential in being a source for rare earth
petroleum and automotive industries, whereas cerium oxide, elements (Costis et al., 2021). The concentration of rare earth elements
lanthanum, and lutetium are widely used in the glass industry to provide in the acid mine drainage samples with solution acidity typically less
polishing color and unique optical properties (Van Gosen et al., 2017). than five can be as high as 130,000 µg/L. Table 3 shows rare earth
Producing permanent magnets from rare earth alloys is an expanding contents of various acid mine drainage samples from different geological
area. Neodymium is used to produce neodymium-iron-boron magnets, locations.
the strongest type of magnet (Uda et al., 2000). These magnets are used Due to the similarities in chemical characteristics, significant rare
to manufacture hard disk drives, speakers, air conditioning compressors, earth content can also be recovered from uranium mining wastes. It is
electric motor production for hybrid cars and wind turbines (Omodara especially a great source of scandium, which is the most valuable rare
et al., 2019). Moreover, gadolinium phosphorous is used for X-ray im­ earth element among the group. An average of 0.2% rare earth oxide has
aging and medical applications such as MRI. Yttrium, lanthanum, and been reported in various uranium mine tailings in Canada, where most
praseodymium are used as pigments for ceramics (Akdogan and Ghosh, uranium deposits are located (Costis et al., 2021). Moreover, electronic
2014). waste has shown significant potential as an alternative rare earth source.
Even though the market prices dropped as a result of source diver­ Recycling rare earths from electronic waste can significantly contribute
sification, the industrial demand is still expected to increase due to the to sustainability and environmental protection (Amato et al., 2019).
expanded area of use and continuous growth in population and tech­ According to 2016 data, 44.7 million tons of electronic waste were
nological use (Guyonnet et al., 2015). Within that context, research and generated globally, which is projected to be even greater in the future
development studies have gained tremendous significance. There have (Jyothi et al., 2020). Although it is not desired to initiate new mining
been studies validating the technical feasibility of coal and coal operations from a sustainability point of view, new operations have been
byproducts as alternative sources for rare earth elements (Akdogan and started in India, Brazil, and Vietnam to produce rare earth as a
Ghosh, 2014; Hower et al., 2016; Kolker et al., 2017; Das et al., 2018; byproduct of rutile and zircon production (Paulick and Machacek,
Huang et al., 2018; Lanzerstorfer, 2018; Lin et al., 2018; Valentim et al., 2017). Meanwhile, Russia and Malaysia began to recover rare earths
2019), in which the rare earth concentrations vary between 270 and from magnesia and cassiterite plants, respectively (Van Gosen et al.,
1,480 ppm (Blissett et al., 2014; Das et al., 2018) with an average of 69 2017). Furthermore, two previously operated mines, Mountain Pass in
ppm on a whole mass basis (Eskanazy, 1987; Karayigit et al., 2000; Hu the U.S. and Mount Weld in Australia, were re-opened to increase their
et al., 2006; Ketris and Yudovich, 2009; Wagner and Matiane, 2018; respective domestic rare earth production. In fact, in 2020, the value of
Huang et al., 2019). It was reported that the rare earths were associated
with the incombustible material in coal rather than the combustible
Table 3
carbon material (Honaker et al., 2016). Alternatively, regardless of the
Summary of rare earth concentrations in different acid mine drainage samples
from various locations (modified from Costis et al., 2021).

Table 1 Location Type of Mine Rare Earth Content

(µg/L)
Some of the rare earth-bearing minerals (modified from Balaram (2019)).
Brazil Uranium 130,000
Mineral Formula
Germany Uranium 4,742
Allanite (Y,Ln,Ca)2(Al,Fe3+)3(SiO4)3(OH) India Coal 169–2,563
Apatite (Ca,Ln)5(PO4)3(F,Cl,OH) USA (Illinois) Coal 85–9,879
Bastnaesite (Ln, Y)(CO3)F USA (West Virginia & Coal Up to 1,139
Eudialyte Na4(Ca,Ln)2(Fe2+,Mn2+,Y)ZrSi8O22(OH,Cl)2 Pennsylvania)
Fergusonite (Ln, Y)NbO4 USA(Appalachia (PA)) Coal Up to 1,240
Gittinsite CaZrSi2O7 USA (Appalachia) Coal 27–34
Kainosite Ca2(Y,Ln)2Si4O12(CO3).H2O USA(West Kentucky) Coal 6,140
Loparite (Ln,Na,Ca)(Ti,Nb)O3 USA (Montana) Polymetallic, Copper 2,688–2,914
Monazite (Ln, Th)PO4 Spain (Poderosa) Pyrite-Copper 7,010–9,700
Mosandrite (Na,Ca)3Ca3Ln(Ti,Nb,Zr)(Si2O7)2(O,F)2 Spain (Esperanza) Pyrite-Copper 900
Parisite Ca(Ln)2(CO3)3F2 Spain (Monte) Zinc-Lead 7,900
Rinkite (Ca,Ln)4Na(Na,Ca)2Ti(Si2O7)2(O,F)2 Spain (Almagrera) Zinc-Lead-Copper 3,500
Synchysite Ca(Ln)(CO3)2F Romania Zinc-Lead-Copper- 1,582
Xenotime (Zr, Ln)SiO4 Silver
Ion-Adsorption Typically aluminosilicate minerals (i.e., Kaolinite, Illite, Cuba Pyrite-Zinc-Lead 370–860
Clay Smectite, etc.) Portugal Gold 14.6–70.4

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D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

rare earth compounds and metals imported by the U.S. decreased by Table 5
almost 30% compared to 2019 (USGS, 2021). New deposits have also Summary of previously performed review studies on rare earth elements, their
been identified in Canada, the United Kingdom, Estonia, Sweden, and sustainability, environmental impact, and current knowledge gaps.
Greenland (Suli et al., 2017). Researchers are also investigating the Primary Focus Gaps for Future Studies
feasibility of using eudialyte, a heavy rare earth-rich mineral, phos­ Hoenderdaal et al. One of the earliest review A considerably thorough
phogypsum, the waste product of the phosphate rock and fertilizer in­ (2013) studies with a particular review study; however, the
dustry, phosphate processing waste clays, apatite, cheralite, and loparite focus on dysprosium. main focus was on a single
as secondary sources for rare earth elements (Dutta et al., 2016; rare earth element, and the
environmental aspect of the
Schreiber et al., 2016; Zhang et al., 2017; Eskanlou and Huang, 2021;
subject was not present.
Costis et al., 2021). Nickel-laterites of Cuba and the Dominican Republic Rim et al. (2013) Compiled the Needed to be updated with
and alluvial deposits of Greece may serve as significant reserves as well environmental and current knowledge of the
(Charalampides et al., 2015; Dutta et al., 2016). A summary of several occupational health effects toxicology of REEs given the
types of potential secondary rare earth element sources is given in of REEs by in vitro and in year that it was published.
vivo studies.
Table 4. McLellan et al. Examined the sustainability No detailed review was
However, one of the challenges facing rare earth mining is the (2014) of the rare earth industry provided regarding the
detectable radioactive matter that both conventional and unconven­ from a social, toxicity of REE extraction
tional rare earth sources contain (Dutta et al., 2016; Pillai, 2017). Some environmental, technical, processes.
and economic perspective.
of the previously conducted review studies on the environmental
Elshkaki and A detailed review of the It lacked details of the
assessment of rare earth processes are summarized and discussed in Graedel (2014) supply and demand of rare environmental aspect; did
Table 5. However, this major issue still has not received the attention it earth, focusing on wind not provide separation
requires except in a few studies (Anon, 2012; Sapsford et al., 2012; power technology; also schemes.
O’Callaghan, 2012; McLellan et al., 2014; Binnemans and Jones, 2015; reviewed the environmental
impacts of REE extraction.
Kumari et al., 2015; Pagano et al., 2015; Wang et al., 2016; Balaram,
Charalampides et al. Summarized the Did not evaluate the
2019; Omodara et al., 2019; Pagano et al., 2019; Su et al., 2020; Jyothi (2015) applications and world environmental impact of
et al., 2020; Judge and Azimi, 2020; Garcia et al., 2020; Xiong et al., reserves of REEs. rare earth extraction
2020). Therefore, the literature gap on rare earth element-associated processes and
predominantly focused on
hazards needs to be addressed in detail. This study targeted providing
Europe.
comprehensive information on the environmental aspect of rare earth Al-Areqi et al. Discussed the issues arising A brief overview of thorium
elements extraction to address the knowledge gap. The subsequent (2015) in Malaysia due to thorium separation techniques, did
section presents detailed information on environmental and health and provided information not cover a full review.
concerns arising from the radioactive elements in rare earth minerali­ on thorium production from Besides, the focus was only
various sources. on the radioactivity issues
zation, considering the traditional and secondary sources. Regulatory
seen in Malaysia.
stipulations were also covered in the next section. Afterward, separation Zhu et al. (2015) A comprehensive review for Mainly focused on the rare
techniques for removing radioactive and hazardous elements from rare the separation of thorium earth-producing mines in
earths were reviewed via centering around the three most commonly and uranium from REEs China. Secondly, the
with various separation manuscript did not address
used methods, i.e., selective precipitation, solvent extraction, and solid-
technologies and examples. secondary sources (i.e., coal
phase extraction. and coal-based materials).
Stegen (2015) Addressed rare earth The details of radioactivity
2. Environmental impact of rare earth extraction and shortages and reviewed in rare earth mineralization
Regulatory stipulations potential remedies, such as were not sufficient.
recycling, new mines,
seabed mines, etc.
As previously indicated, rare earth mining faces challenges due to Pagano et al. (2015) Primarily focused on REE Focused solely on the
and Pagano et al. occupational exposure, negative impact of
(2019) human health effects, and individual REEs, not
Table 4 REE toxicity on animal impurities associated with
health. REEs (i.e., radionuclides).
Potential secondary sources of rare earth elements.
Abdel-Razek, et al. Performed a study on Focused only on monazite
Mineral or Source Chemical Formula Rare Earth (2016) radiation exposure that mineral.
Oxide (wt%) occurred during the
separation of REEs.
Apatite [(Ce)Ca5(PO4)3(OH,F, ~1
Dutta et al. (2016) Provided a detailed study on No details of the
Cl)]
extraction methods, occurrences, potential
Cheralite (Ca,Ce,Th)(P,Si)O4 1–10
sustainability of the supply harm, or separation
Red Mud [ɑ-AlO(OH)] 130–390 ppm
chain, secondary sources for possibilities of radioactive
Sc
REEs. elements.
Zircon (Zr,REE)SiO4 less than 3
Nassar et al. (2016) Compiled the metal The focus was only on the U.
Sphene (Ca,REE)TiSiO5 less than 3
requirements for U.S. S. and did not present a
Fluorite (Ca, REE)F2 –
electricity generation (i.e., global review.
Fluocerite (Ce, La) (CeLa)F3 –
REEs and others).
Loparite (Ce,Na,Ca)(Ti,Nb)O3 –
Findeib and Schaffer A thorough review of rare Focused mostly on the
Eudialyte Na4(Ca,Ce)2(Fe2+,Mn2+, 1–10
(2017) earth mining residues’ primary rare earth minerals
Y)ZrSi8O22(OH,Cl)2
impact, separation with information on the
Allanite (Ce) (Ce,Ca,Y)2(Al,Fe2+, 3–51
techniques, and regulatory secondary sources and their
Fe3+)3(SiO4)3(OH)
approaches. radioactivity lacking.
Allanite (Y) (Y,Ce,Ca)2(Al, 3–51
Wang et al. (2017) Included separation Predominantly focused on
Fe3+)3(SiO4)3(OH)
processes for thorium in the remediation techniques
Phosphogypsum – 0.01–2
addition to the in China without covering
Coal and Coal By-products – 0.027–14.8
measurements taken the radioactivity and the
Electronic Waste (i.e., permanent – –
magnets, fluorescent light bulbs, (continued on next page)
metal alloys, etc.)

3
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Table 5 (continued ) Navarro and Zhao, 2014; Dutta et al., 2016). For example, at the Bayan
Primary Focus Gaps for Future Studies Obo Mine, the largest mine in China, rare earths are produced as a
secondary product of iron ore, and the concentrations of ThO2 and U3O8
towards cleaner rare earth environmental impact of
production in China. REE processes in depth.
are 0.01–0.05% and 0.0005–0.002%, respectively (Liu and Pan, 2011).
Garcia-Tenorio et al. A comprehensive Focused on a specific mine In that mine, typically, 200 tons of thorium dioxide sludge are produced
(2018) radiological evaluation of a in Spain. Only pre- every year from 100 thousand tons of rare earth concentrates. Also,
pre-operational grey operational evaluation was according to an early study conducted at the same mine by Baotou Ra­
monazite mine. conducted without
diation and Environmental Institute, the radioactivity at the plant and in
operational data.
Jaffary et al. (2019) Carried out the radiological A comprehensive study for the soil was 32 and 1.7 times higher than the normal range. Typically,
assessment of a Malaysian the studied sample, the uranium concentration in soil is between 0.3 and 11.7 mg/kg, and
monazite mine and its however, only specific to the average radioactivity of 234U is between 0.02 and 0.04 Bq/g (Abdel-
processing residue. one particular sample. Sabour, 2014). Likewise, the thorium content in the leaching pond was
Balaram (2019) Reviewed the occurrences, Did not include the
deposit types, applications, separation methods for the
around 5 mg/L, while the thorium concentration in freshwater was 0.01
extraction methods, and the removal of hazardous to 1 µg/L (Findeiß, 2016). In another study, it was reported that the
environmental impact of impurities. radiation level in the Bayan Obo city areas was in the range of 100–150
REEs. nGy/h, which was 50% higher than the accepted value. This range later
Adeel et al. (2019) Examined the effect of REEs Focused only on the
increased to 600–2000 nGy/h at mining sites (Liu and Pan, 2011).
on the aquatic system, negative effects of REEs on
human, and animal health. natural resources and living Similar high radiation activity results were reported in Wang and his
mechanisms and did not coworkers’ (2016) study as well. According to the measurements made
review the effects of in the vicinity of the Bayan Obo mine, the 232Th activity in total sus­
impurities seen alongside. pended particulates in mining and smelting areas was 820–39 µBq/m3,
Amato et al. (2019) One of the latest studies The environmental impact
discussed the innovative of these innovative rare
and 720 µBq/m3 respectively, which is significantly higher than the
advances in REEs from a earth solutions from a world limit of 0.5 µBq/m3.
sustainability point of view. sustainability perspective The chemical extraction of rare earths from monazite involves
Recycling techniques and was not included while only occupational radiation exposures in the range of 0.13–1 mSv per ton,
life cycle assessments were compiling the recycling
depending on the concentration of monazite (Pillai, 2017). Other re­
also included. efforts, mainly in Europe.
searchers studied thorium and uranium activity in a monazite mine in
Spain and observed an activity range of 70–100 Bq/kg and 40–60 Bq/kg
detectable radioactive matter. Both coal and traditional rare earth- for thorium and uranium, separately (Garcia-Tenorio et al., 2018). The
bearing minerals currently processed contain a considerable amount radioactivity and chemical characterization of Malaysian monazite
of thorium and uranium due to isomorphic substitution. Therefore, it processing residue was comprehensively investigated in Jaffary, and his
needs to be appropriately treated to prevent their interaction with coworkers’ (2019) study, which clearly pointed out that the radioac­
groundwater and distribution to the air. In some cases, in addition to tivity is above world permitted limits. Simalarly, Aziman and Ismail
isomorphic substitution, uranium is also formed by epigenetic infiltra­ (2020) conducted a study to emphasize the high radioactivity level of
tion during the lignite-subbituminous stage of coalification (He, 2014; water leach residue after processing monazite in Malaysia. For these
Ault et al., 2015; Findeiß, 2016; Qin et al., 2018; Kursun et al., 2018). If reasons, countries like Australia and the United States stopped rare earth
not regulated correctly, exposure to such elements may develop cancer production from monazite in the early 90 s (Hedrick, 2000; Schuler
risk for workers, severely damage surface vegetation, cause water et al., 2011). Natural levels of radioactivity in solid waste produced from
pollution, and affect agricultural output. rare earth beneficiation processes are given in Table 7.
It was reported that bastnaesite contains up to 0.3 wt% thorium di­ As an unconventional resource for rare earth production, coal also
oxide and 0.09 wt% uranium dioxide. In contrast, monazite’s thorium contains a significant amount of thorium and uranium either associated
and uranium contents can be as high as 20 wt% and 16 wt%, respec­ with elements in the coal itself or within the minerals that are part of
tively. Similarly, xenotime may contain up to 5 wt% uranium dioxide coal formation (Cooper, 2005; Papastefanou, 2007; Department of En­
(Van Gosen et al., 2017). In other words, concentrations of 238U and ergy, 2017; Lange et al., 2017; Dai and Finkelman, 2018). Besides
232
Th in these minerals exceed 1000 Bq/kg (Liu and Pan, 2011). Table 6 thorium and uranium, their decay products, such as radium and radon,
summarizes the rare earth oxide, thorium, and uranium contents of are also present in coal-related materials, raising more severe concerns
three major rare earth-bearing minerals in detail. since they have approximately ten times higher radioactivity than
The rare earth extraction processes can yield approximately 1.4 tons thorium and uranium (USGS, 1997). While the daughter-nuclides decay
of radioactive waste in the form of solid, liquid, or gas for one ton of rare with α- ß- and γ-radiation, thorium and uranium emit α-radiation which
earth oxide (Jiabao and Jie, 2009; British Geological Survey, 2011; has more substantial radio-biological impacts due to the short travel
distances of alpha radiation in the air as opposed to ß- and γ-radiation
(Findeiß, 2016). Radon is especially unique among the decay daughters
Table 6 because it is a colorless, odorless, tasteless gas and may quickly
Rare earth oxide, thorium, and uranium contents of primary rare earth sources distribute to the atmosphere. Its decay starts with 218Po, continues with
214
(Modified from Zhu et al., 2015). Pb, 214Bi, and ends with 214Po. If proper ventilation is lacking, serious
Mineral Chemical Rare Earth Oxide, ThO2, wt UO2, wt radioactivity problems may occur in the mine (Holden and Burchfield,
Type Formula wt% % % 2010; Barakos et al., 2014). Moreover, many condensed elements with
Bastnaesite (Ce,La)(CO3)F 70–74 0–0.3 0.09 high volatility (i.e., As, Cd, Cu, Pb, etc.) are also present on the surface of
(La,Ce)(CO3)F fly ash samples (Parzentny and Rog, 2019).
Y(CO3)F The study conducted by Finkelman (1999) with approximately 7000
Monazite (Ce,La,Nd,Th) 35–71 0–20 0–16 coal samples indicated that the average thorium and uranium concen­
PO4
(La,Ce,Nd,Th)
trations in coal as 3.2 and 2.1 ppm, respectively. Another study con­
PO4 ducted by Dai et al. (2014) also revealed a certain amount of uranium in
(Nd,Ce,La,Th) coal samples taken from deposits in China and Russia. Arbuzov and his
PO4 coworkers (2011) performed a detailed study on radioactive elements in
Xenotime YPO4 52–67 0–5
–
coal and peat with >5000 samples collected in Northern Asia,

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D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Table 7
Level of radioactivity in solid waste generated from rare earth beneficiation processes (modified from Liu and Pan (2011).
Uranium (Bq/kg) Ra-226 (Bq/kg) Thorium (Bq/kg) External ɤ Dose Rate (nGy/h)

Average Maximum Average Maximum Average Maximum Average Maximum

2081 83,044 1240 53,700 4786.3 85,600 3249 48,344

specifically, Siberia, Russian Far East, Mongolia, and Kazakhstan. The

Table 8
average uranium and thorium contents for the studied locations changed
Thorium and uranium concentration in the world’s selected coal and coal-based
between 0.6 and 32.8 ppm and 0.8–9.2 ppm, respectively. According to
materials (modified from Parzentny and Rog (2019)).
a characterization study conducted by the United States Geological
Survey (1997) with approximately 2000 U.S. coal samples, the con­ Type of Material Country/ Thorium Uranium
Area (ppm) (ppm)
centration of thorium and uranium has been found to mainly vary be­
tween 1 and 4 ppm, with the highest concentration value of 20 ppm Raw coal Bulgaria 6 5
Poland 3.2 1.9
being reported in some cases. It was reported that uranium organically
Poland 2.3 1.9
bounds within the coal and may be associated with other minerals such USA 3.2 2.1
as rare earth phosphates (Finkelman et al., 2018). USA 1.5–5.9 1.2–3.9
Even though the initial concentration of thorium and uranium in coal China 5.84 2.43
and coal byproducts is not high compared to their existence in tradi­ China NA 0.75–7207
Feed Coal (the coal before Europe 5.6 6.1
tional rare earth minerals, the radioactive elements can be substantially burning) Europe 17–65 5–29
enriched along with the processing stages and may present in the solid, Brazil 14.09–17.04 6.12–7.67
liquid, or gaseous wastes. The decay products or heavy metals may be Poland 1.1–2.6 0.2–0.8
released during earlier stages, such as blasting, crushing, and grinding Spain 5.6 6.1
Turkey 9 14
steps, and can cause lung cancer (Findeiß, 2016). Moreover, the radio­
Fly ash Europe 22.1 22.9
nuclides may accumulate in the upper layer of the soils, form complexes Brazil 33.5–42 14.5–24.8
with organics, and be moved into water streams or air (Abdel-Sabour, China 5.8–50 2.6–51.9
2014). Complexes of these radioactive matter become more soluble Poland 23 10.6
under acidic conditions, and they may be transported through soil and Poland 7.6–19.3 3.3–10.6
Spain 22.1 22.9
plants and enter the food chain. When these toxic ions enter living or­ Turkey 22 34
ganisms, such as the human body, they accumulate in the liver, spleen, USA 14.0–28.0 6.9–12.7
and marrow, precipitating their hydroxide forms (Metaxas et al., 2003). USA 11.8–21.6 6.72–10.4
Therefore, dust minimization and well indoor ventilation have extreme Bottom ash Europe 20.6 19
Australia 15–42 5–9.7
importance. It was stated that when coal is burned into fly ash, it creates
Brazil 25.8–42.9 9.3–16.7
a concentrated form of thorium and uranium with a concentration China 19.1–25 8.5–379.2
approximately ten times higher than the initial level (Hvistendahl, Spain 20.6 19
2007). Although the direct toxicity of thorium is low because of its Turkey 15 19
stability under ambient temperature, the fine thorium powder is self- USA 14.9–25.3 0.9–9.7
USA 13–25.3 5.87–9.83
ignitable (Metaxas et al., 2003). It is noteworthy that acid mine
drainage (AMD) sludge has low concentrations of thorium and uranium
(Vass et al., 2019). Vass et al. (2019) studied several AMD sludge sam­ river close to a mine site is subsequently reduced. On the other hand, in
ples and reported an average of 5.67 and 4.46 ppm thorium and uranium Malaysia, two rare earth processing plants were closed due to the issue
concentration, respectively. Parzentny and Rog (2019) performed a of disposing of a vast amount of naturally occurring radioactive material
detailed study on the role of mineral matter in concentrating thorium wastes (Al-Areqi et al., 2016).
and uranium in coal and combustion residues. The researchers also For thorium and uranium, radioactivity with less than 1 Bq/g is
summarized the thorium and uranium contents of a wide variety of coal considered nonradioactive in every process material, and the waste is
and coal-based samples worldwide (Table 8). The level of radioactivity classified as exempt waste. This limit is valid for all thorium and ura­
in the solid waste generated from coal processing is also given in Table 9. nium decay products (Haridasan, 2013). On the other hand, the NORM
In terms of regulatory approaches, various standards and rules need exposure limit occurring due to uranium and rare earth mining is set as
to be followed to dispose of these radioactive wastes or control and 1 mSv/year for gamma exposure and 10 mSv/year for radon inhalation
prevent their exposure depending on the mine source (i.e., uranium (IAEA, 2013). Although some of the uranium mines may have higher
mine or rare earth mine, etc.). When naturally occurring radioactive radon concentrations, in general, the radon concentrations are less than
materials are concentrated or released by human activities (i.e., mining), 100 Bq/m3, and typically, the NORM exposure occurring due to the
they are classified as technologically enhanced naturally occurring processing of other materials is less than 1 mSv. Moreover, radioactive
materials (TENORM) (Findeiß, 2016). The International Atomic Energy materials with less than 50 ppm of uranium and thorium or any com­
Agency (IAEA) has specific guidelines for these materials used by many bination of the two are regarded as not radioactive by the U.S. Nuclear
countries. For example, as sustainable and cleaner production becomes Regulatory Commission. Additionally, according to the World Health
more stringent in recent years, China started implementing stricter Organization, the maximum uranium level in drinking water can not
standards to develop environmentally favorable industrial practices exceed 15 µg/L, and the maximum contaminant level set by the Envi­
(Wang et al., 2017). The IAEA’s safety standards were begun to be fol­ ronmental Protection Agency is 20 µg/L (Rozmaric et al., 2009; Cama­
lowed as a national standard for rare earth mining in 2003 to prevent cho et al., 2010). According to the Canadian Soil Quality Guidelines, the
ionizing radiation (Liu and Pan, 2011). Again in China, an environ­ maximum allowable concentrations of these hazardous elements are 23
mental impact assessment approved by Environmental Protection ppm for agricultural and residential land use, 33 ppm for commercial
Agency (EPA) is requested at non-uranium mining sites containing land use, and 300 ppm for industrial land use. (Abdel-Sabour, 2014).
natural radioactive nuclides. Similarly, improved effluent treatment In rare earth mining sites, thorium and uranium-containing leaching
processes are applied in India, and the radionuclide concentration in the wastes are generally neutralized with limestone before their disposal. If

5
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Table 9
Level of radioactivity in solid waste generated from coal processing (modified from Liu and Pan (2011)).
Uranium (Bq/kg) Ra-226 (Bq/kg) Thorium (Bq/kg) External ɤ Dose Rate (nGy/h)

Average Maximum Average Maximum Average Maximum Average Maximum

225 7600 326 92,178 91 910 162 987

the radionuclide-containing waste is in the form of a solid, it must be 2016).

kept wet by sprinkling the stockpiles to minimize dust formation.
Additionally, impoundment facilities are built with waterproof mate­ 3.1. Selective precipitation
rials like high-density polyethylene (HDPE) to prevent interference with
soil and groundwater where the radioactive element containing tailings Selective precipitation of elements by controlled pH is the most well-
of rare earth mining are mixed with barium hydroxide ([BaOH]2) to known method for removing impurities from leach liquors. Besides, it
precipitate those elements (Findeiß, 2016). The Australian company has advantages of being a cost-effective and straightforward operation
Lynas stores their thorium-containing waste solutions generated from to perform and manage (Monhemius, 1977; Zhou et al., 2018). The
the water leach process in ponds lined with HDPE. Another consider­ underlying mechanism of precipitation is reacting chemicals with ions to
ation is reducing the concentration of radioactive materials to less than generate insoluble complexes, which can then be separated from
500 ppm, which is the internationally maximum allowed concentration aqueous solutions by filtration (Zhou et al., 2018). Precipitation is
limit to dispose of the waste without restriction. One way to do that is by induced by complexation using hydroxides or sulfides (Hostetler and
mixing radioactive waste with other residues to lower the concentra­ Garrels, 1962). In the case of rare earth purification, it takes advantage
tions of thorium and uranium (Findeiß, 2016). At Mountain Pass mine, of different precipitation pH ranges for thorium, uranium, and rare
this procedure is followed, and the regular mining and milling tailings earths (Vijayalakshmi et al., 2001; Silva et al., 2018).
are co-disposed with radioactive wastes. In Kim and Osseo, 2012 study, it was stated that the dissolved species
Separated thorium and uranium have significant potential to be used of thorium, uranium, and rare earth metals in acidic solutions might be
in the fuel cycle or electricity production by nuclear energy. The U.S. separated by pH adjustment in which thorium separation is expected to
Department of Energy estimates an approximately 28% increase in the take place first. This also agrees with other literature indicating different
need for electrical power from 2012 to 2040 (Nandanwar et al., 2016). precipitation pH ranges for thorium, uranium, and rare earths. Zhu et al.
According to 2015 data, 87,000 tons (174 million pounds) of uranium (2015) carried out a detailed review to address the environmental
(in the form of U3O8) was used in nuclear power plants worldwide, and a impact and association of thorium and uranium. As indicated in the
continuous increase is projected (Kim et al., 2016). The depleting ura­ study, in chloride media, thorium’s precipitation pH range is typically
nium sources create a need for substitutes (Udayakumar et al., 2021). 2.5–5.5; following this, uranium and rare earth precipitations subse­
Aziman and Ismail (2020) have a thorough review study in which they quently take place. The precipitation pH range of uranium and rare
investigated the sustainable recovery of thorium from the water leach earths is approximately 5.5–7 and 6.8–8, respectively (Langmuir, 1978;
residue of rare earth processing. Thorium has three to five times more Zhu et al., 2015). On the other hand, a shift in the precipitation pH
potential reserves than uranium, and 232Th can be converted to 233U by ranges is expected when the solution medium changes. While in sulfide
absorbing slow neutrons (Kursun et al., 2018; Salehuddin et al., 2019). medium, precipitation of these elements occurs at lower pH values, in
By converting thorium to uranium, thorium can effectively replace nitrate medium, insoluble complexes are formed at slightly higher pH
uranium-based nuclear reactors and become an alternative to uranium values than chloride medium (Zhu et al., 2015; Garcia et al., 2020).
sources (Xiong et al., 2020). Therefore, if the standards are met, thorium However, variations may be seen depending on the elemental compo­
and uranium separated from rare earth elements can create an addi­ sition of the solutions and the concentration of the precipitation reagent
tional production source. used.
Thorium, with its only oxidation state, 4+, is relatively easy to work
3. Solution purification techniques to remove thorium and with compared to other actinide elements, such as uranium, because of
uranium from rare earth elements the simplicity of the species (Torapava et al., 2009). Th4+ is also the
largest tetravalent cation with a radius of approximately 1 Å. On the
The enrichment of rare earth elements requires a complex and other hand, uranium can be seen in many forms (i.e., U (III, IV, V, VI))
detailed processing scheme. In general, hydrometallurgical processing and form various complexes such as oxides, phosphates, carbonates, etc.
techniques with various chemical compounds are applied. Typically, (Navrotsky et al., 2013). Uranium (IV and VI) are the most common and
bastnaesite and monazite are first subjected to sample preparation and stable states (Monji et al., 2016). While U(VI) occurs in oxidizing con­
pre-concentration, including size reduction, roasting, froth flotation, ditions, it is seen in the form of U(IV) in reducing conditions (O’Calla­
which are later followed by dissolution with a strong acid (Yang et al., ghan, 2012). Chemical reactions governing the precipitation behavior of
2020). Physical and chemical methods to recover rare earths are well REEs3+, Th4+, and U6+ are given below (Silva et al., 2018). While most
documented (Ozbayoglu and Atalay, 2000; Kim and Osseo-Asare, 2012; of the rare earths are usually in the form of trivalent cations, some of
Jordens, 2016; Anderson et al., 2017; Suli et al., 2017; Zhang and them may have divalent or tetravalent states as well (Charalampides
Honaker, 2018; Honaker et al., 2019; Zhang and Honaker, 2019). et al., 2015).
However, as described earlier, thorium and uranium are also enriched
alongside rare earths. Especially after leaching rare earths with acids, REEs3+ −
(aq) + 3OH (aq) →REEs(OH)3(s) (1)
such as sulfuric acid (H2SO4), hydrochloric acid (HCl), or nitric acid
(HNO3), these hazardous elements also dissolve, which in return, re­ Th4+ −
(aq) + 4OH (aq) →ThO2(s) + 2H2 O (2)
quires further purification of the leachate. Although many remediation
solutions are known, only a few are feasible for a large-scale operation. UO2+ −
2(aq) + 2OH (aq) →UO2 (OH)2(s) (3)
This review manuscript focused on precipitation, solvent extraction, and
ion exchange-adsorption processes since they are the most widely used A recent experimental study conducted by Talan and Huang (2020)
techniques for removing radioactive elements from rare earths (Flett, produced coherent results with the literature. Around pH 4.8, 100% of
1992; Chellam and Clifford, 2002; Akkaya, 2013; Zhang and Zhao, the thorium content in a highly acidic (6 mol/L HCl) solution precipi­
tated using 2 mol/L sodium hydroxide (NaOH), and no thorium content

6
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

was detected in the remaining solution. A further increase in the pH Al-Areqi et al., 2016 studied selective precipitation of thorium from
resulted in a significant amount of rare earth element and uranium co- sulfuric acid digested (H2SO4 at > 200 ◦ C) Malaysian monazite sample
precipitation, >30% and 95%, respectively. The observed phenomena using 13.4 mol/L ammonia. At pH 1.08 to 1.89, Al-Areqi and his co­
can be attributed to the fact that the precipitation pH range of uranium workers achieved 98% thorium separation. Differently, Silva et al.
(i.e., 5.5–7) and rare earths (i.e., 6.8–8.0) overlaps to some degree, (2019) used calcium carbonate to adjust the pH and precipitated
which leads to the co-precipitation of the two. Similar results were ob­ thorium from sulfate solutions. In this study, in addition to thorium
tained when magnesium oxide and lime were used as the neutralizing separation, high uranium precipitation (approximately 65%) was also
agent. Mackowski et al. (2011) achieved thorium precipitation and achieved by increasing the solution pH to a value of 5.
minimal rare earth co-precipitation from a monazite sample using lime On a larger scale, at the Bayan Obo Mine, the high iron content is
at pH 2.5. In Zhu et al. (2006) and Krebs and Furfaro’s (2013) studies, separated at the magnetic separation step. The remaining tailings are
98% and 100% thorium precipitation were seen at pH 4 and 4.8 in sent to the rare earth element concentration circuit, where the rare earth
sulfide and chloride media, respectively. Krebs et al. (2013) study also elements are beneficiated using a combination of physical and chemical
observed almost 72% of uranium precipitation at pH 4.8. However, processes. Following froth flotation, the ore is roasted then treated with
while Krebs and Furfaro used conventional rare earth minerals as the leaching. Hydrochloric acid is used to dissolve both rare earths and
feedstock, Talan and Huang’s study was conducted with coarse coal thorium; later, the rare earth-chloride-containing solution is transferred
refuse, leading to the difference observed in uranium precipitation. to a multistage solvent extraction circuit for individual separation
Besides, in Talan and Huang’s study, no substantial difference was (Schreiber et al., 2021). In China’s second-largest rare earth mine,
observed in the precipitation recovery of thorium, uranium, and rare Sichuan Mine, the ore is roasted at a temperature > 500 ◦ C, where
earths when three alkaline precipitation reagents (i.e., sodium hydrox­ thorium and cerium are converted to ThO2 and CeO2. The ore is then
ide, potassium hydroxide, and ammonia) were used. In another study, dissolved using hydrochloric acid, where ThO2 and CeO2 remain in the

Fig. 1. Alkali breakdown-RE and Th oxalate precipitation-selective separation process followed by Amer et al. (2013).

7
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

leach residue while the other rare earths are selectively leached to the where the single valence M+ ion can be NH4+, K+, or Na+. Arafura
solution. Later, caustic attack and hydrochloric acid leaching are applied Resources of Australia utilized this process to separate uranium from
to further separate thorium from cerium (Zhu et al., 2015). At Mountain rare earths with double salt precipitation (Na2SO4), where uranium
Pass Mine, bastnaesite is leached with dilute hydrochloric acid, which stays in the solution. It is targeted to leave a portion of thorium into the
also dissolves uranium along with rare earths. The dissolved uranium is solution, where it can be further removed from uranium via precipita­
then selectively precipitated using barium chloride or sodium sulfate tion if required. The amount of thorium precipitated together with rare
(Findeiß, 2016). Another example for separation by precipitation is the earths during double salt precipitation can be subjected to redissolution
Alwaye Project in India, where the ore is leached with hydrochloric acid, with a concentrated hydrochloric acid solution at pH 1–1.5 and
later thorium is precipitated using sulfuric acid in the form of sulfate, neutralize with a basic solution at pH 4–5 to selectively remove thorium
and the rest of the solution contains rare earth elements and uranium. from rare earth elements (Lockyer, 2014; Zhu et al., 2015). The sche­
In addition to the typical precipitation method of adjusting the so­ matic representation of the process is given in Fig. 2.
lution pH, oxalic acid has been frequently employed to initially co-
precipitate thorium and rare earths to separate them from uranium.
The precipitate is subsequently subjected to selective dissolution to 3.2. Solvent extraction
further separate thorium from rare earths using a hot sodium carbonate
solution. Amer et al. (2013) followed this process in which alkali Solvent extraction has been the most extensively used method for
breakdown of monazite was first achieved and followed by dissolution- solution purification due to its ability to handle large volumes of
oxalate precipitation to leave uranium in the solution (Fig. 1). The so­ aqueous solutions (Asselin et al., 1949; Hidayah and Abidin, 2017). It
lution used throughout the study was prepared using sulfuric acid with a has also been an effective technique to remove hazardous matters from
solid to liquid ratio of 1:1.5 at 85 ◦ C. After treatment with 30% oxalic rare earths (Brown and Sherrington, 1979).
acid at elevated temperature (60 ◦ C) at pH 0.7, the precipitation effi­ One of the crucial parameters in the solvent extraction process is the
ciencies of rare earths and thorium reached 99%. Oxalate precipitation type and concentration of the extractant (organic chemical) since the
reactions of rare earth elements, thorium, and uranium in sulfate media efficiency of the procedure depends significantly on the extractant’s
are given in the reactions (4)–(7). Later, thorium separation can be ability to transfer metal ions between two immiscible phases; aqueous
achieved by dissolving the precipitated solid in a carbonate-containing and organic (Hidayah and Abidin, 2017; Zhou et al., 2018). Organic
solution (i.e., Na2CO3 and NaHCO3) at 75 ◦ C, where thorium will phosphorus acid, carboxylic acid, tertiary and quaternary amines, and
create a soluble complex according to the reaction (8), and the rare sulphoxide are some of the commercially used extractant types, which
earths will stay as insoluble. A similar use of carbonate compounds was have been proved to be effective for the separation of radioactive ele­
also stated in another study where Na2CO3 was applied to wash the rare ments while present with rare earths (Palmieri, 1987; Gupta et al., 2002;
earth carbonates at 20 ◦ C, which originated from a sulfate leach solu­ Belova et al., 2015; Zhu et al., 2015; Giri and Nath, 2016; Kuang et al.,
tion. By this method, approximately 98% of thorium was redissolved 2017). However, most of these extractants are also effective for recov­
back into the solution and successfully separated from the rare earth ering rare earths. Therefore, developing a unique experimental scheme
elements (Zhu et al., 2015). for the desired selectivity and separation efficiency is crucial.
Many studies have been conducted to investigate the impact of
REE2 (SO4 )3 + 3H2 C2 O4 →REE2 (C2 O4 )3(s) + 3H2 SO4 (4) different extractant types, diluents, and operating conditions on
removing thorium and uranium from traditional rare earth-bearing
Th(SO4 )2 + 2H2 C2 O4 →Th(C2 O4 )2(s) + 2H2 SO4 (5) minerals (Nasab, 2014; Samsonov et al., 2015; Lu et al., 2016; Wang
et al., 2017). One of the earliest studies in this field was conducted by
UO2 (SO4 ) + H2 C2 O4 →UO2 (C2 O4 )(s) + H2 SO4 (6) Hughes and Singh (1980), who used a secondary amine (Adogen 283) to
separate thorium from monazite and achieved a thorium dioxide grade
UO2 (C2 O4 ) + 3H2 SO4 →UO2 (SO4 )(s) + 2CO2 + 3H2 O (7) of >99% from the strip solution. On the other hand, Amaral and Morais
(2010) studied the removal of thorium and uranium from sulfuric leach
liquor generated from monazite leaching using a mixture of primary and

Th(C2 O2 )2(s) + 4Na2 CO3 + 2NaHCO3 →Na6 Th(CO3 )5 + 2Na2 C2 O4(s) + H2 O + CO2 (8)

Double salt precipitation with sodium or sulfate is an alternative tertiary amine (Primene JM-T and Alamine 336) extractants to observe
method frequently used in the United States and China; however, this the synergetic extraction. A combination of primary and tertiary amines
method is typically employed to separate cerium from the rest of the at one step can help the mutual separation of thorium and uranium and
trivalent rare earth elements. Although some studies report thorium contribute to the economic aspect of extraction circuits by reducing the
precipitation as high as 80%, other studies state lower thorium precip­ number of steps required. During their study, high extraction recoveries
itation (25–30%) (Zhu et al., 2015). Meantime, thorium’s ability to form were obtained for thorium and uranium (>99% for both) while co-
double salts is limited, but it can be co-precipitated and then further extracting only 0.1% of the rare earth elements. The expected re­
separated. In the case of uranium, the co-precipitation depends on actions between primary amine and thorium and tertiary amine and
uranium’s nature in solution. If uranium is in the form of U(VI), its co- uranium are separately given in reactions (10) and (11). These two re­
precipitation is even lower than what is observed for thorium. On the actions are also the foundation of the AMEX process developed in the
other hand, if it is in the form of U(IV), its co-precipitation with cerium 1950 s to remove thorium and uranium from rare earth elements in
can be very high. Therefore, this method varies depending on the sulfate leachate. Following the extraction of thorium via primary
operational conditions and ore characteristics. The chemical reaction extractants, nitric acid is used as the strippant. Differently, for uranium,
representing the rare earth double salt precipitation is given in reaction sodium carbonate is used as the stripping agent (Garcia et al., 2020).
(9). Although Hughes and Singh (1980) stated more thorium and uranium
introduction to the system is inevitable when primary amines were used
M + + RE3+ + 2SO2−4 + XH2 O→MRE((SO)4 )2 .XH2 O (9)

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D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Fig. 2. Double salt precipitation process followed by Arafura Resources of Australia (Zhu et al., 2015).

Fig. 3. Extraction of thorium and uranium with Primene JM-T and Alamine 336, respectively, under various extractant concentrations (Amaral and Morais, 2010).

9
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

to prevent the co-extraction of the lanthanides, Amaral and Morais’ order is UO22+ > Th4+ > REE3+. When present with the three ion
(2010) study reported a selective extraction between thorium, uranium, groups, TBP forms complexes with the ions in the solution according to
and rare earths when Primene JM-T and Alamine 336 were used as the their distinctive capabilities to bind with the extractant (Rand et al.,
extractants with significantly low rare earth co-extraction (Fig. 3). 2008). Similarly, Nasab (2014) observed that uranium extraction is
more feasible than thorium in a chloride medium, attributed to the
4RNH2 H + HSO−4 + (Th(SO4 )4 )− →(RNH2 H + )4 (Th(SO4 )4 )4− + 4HSO−4 (10) species formed between uranium and hydrochloride that TBP readily
extracts by forming soluble organic complexes. On the other hand,
4R3 NH + HSO−4 + (UO2 (SO4 )3 )4− →(R3 NH + )4 (UO2 (SO4 )3 )4− + 4HSO−4 thorium purification by solvent extraction in nitric acid media is more
(11) favorable over rare earth elements (Menzies and Rigby, 1961; Al-Areqi
Even though tertiary amines are more preferential for uranium et al., 2014). Nitrate is a preferred medium for enhanced extraction of
removal and primary amines are more selective towards thorium in thorium due to an associated increase in the hydration energy of the
sulfuric acid media (Shimidt, 1971), in Borai and his coworkers’ (2014) anions (Nasab, 2014; Lu et al., 2016).
study, a primary amine was reported to be the most efficient one to­ Tris(2-Ethylhexyl) phosphate (TEHP) and tri-iso-amyl phosphate
wards both thorium and uranium. While 90% of uranium extraction (TiAP) are other neutral organophosphorus extractants, which are
using 0.1 mol/L Octylamine at pH 4 was achieved, thorium extraction typically dissolved in n-paraffin or xylene, as opposed to kerosene.
was higher (97%) and required lower chemical concentration (0.01 Biswas et al. (2013) performed a comparative study to remove thorium
mol/L) and pH value (3). However, when the system was changed to a and uranium from a monazite sample using TBP and TEHP. The process
multielement system, tertiary amines were more favorable for the flowsheet followed during their research is given in Fig. 4. Hot alkali
extraction of thorium and uranium. As a result, 80% of thorium sepa­ digestion of monazite occurs, followed by washing with water to sepa­
ration was achieved using 0.01 mol/L N,N-dimethyl aniline at pH 4. On rate thorium, uranium, and rare earth elements as their hydroxide form.
the other hand, 66% of uranium removal was reported using 0.1 mol/L Later, selective dissolution of rare earth elements is targeted using hy­
extractant at pH 7 (Borai et al., 2014). drochloric acid at pH 3, where thorium, uranium, and a portion of rare
Another type of extractants commonly used are acid organophos­ earths stayed as insoluble compounds and later dissolved separately
phorus, including Cyanex series, di-(2-Ethylhexyl)-phosphoric acid using 2–3 mol/L nitric acid. Subsequently, solvent extraction steps were
(DEHP), (2-Ethylhexyl) 2-Ethylhexyl-phosphonic acid (EHEHP), and di- employed, and>99% of uranium was separated using 0.2 mol/L TEHP in
(2-Ethylhexyl) 2-Ethylhexyl phosphonate (DEHEHP) (Garcia et al., a multistep circuit.
2020). Gupta et al. (2002) investigated thorium and uranium separation UO2+ −
(14)
2 + 2NO3 + 2X→UO2 (NO3 )2 .2X
from rare earths using Cyanex 923. Furthermore, Nasab et al. (2011)
studied thorium removal using Cyanex 272 and Cyanex 302 as the Th4+ + 4NO−3 +3X→Th(NO3 )4 .3X (15)
extractants. Although good selectivity and high purity were achieved in
the study conducted by Gupta et al. (2002), Nasab used the other forms When the extraction is completed, the extractant is stripped by
of Cyanex extractants to minimize the multistage stripping for Cyanex mixing the solution with acids. This step removes ions from the organic
923. One drawback of the Cyanex series is that they require high acidity, phase, draws them into the aqueous acids, and regenerates the extrac­
rendering them infeasible for industrial-scale applications from an tant (Jorjani and Shahbazi, 2016). Talan and Huang (2020) examined
economic standpoint. The extraction of thorium and uranium with the difference between DI water and sulfuric acid in stripping efficiency.
Cyanex extractants occur according to the following reactions, where R They stated that the stripping agent is not a significant parameter on the
represents the extractant: separation of uranium from rare earth aqueous solution, at least for the
studied two solutions. In the researchers’ study, the lowest uranium
Th4+ + 4NO−3 +3R→Th(NO3 )4 3R (12) recovery of 1.8 wt% into the final rare earth product stream was ach­
ieved under the conditions of 50 v% TBP, feed pH at 3.5, organic to
UO2+ −
2 + 2NO3 + 2R→UO2 (NO3 )2 2R (13) aqueous phase ratio at 3, and 1 mol/L sulfuric acid as the strippant.
Tributyl phosphate (TBP), a neutral organophosphorus extractant, is Similarly, Biswas et al. (2013) used water to strip uranium-loaded
also indicated as an effective extractant for thorium and uranium sep­ extractant phase and achieved good recovery (>99%) in three strip­
aration. Extraction reactions of thorium and uranium when an organo­ ping stages with the organic to aqueous phase ratio of 1:1. In some cases,
phosphorus extractant is used are given in reactions (14) and (15). a combination of two processes can be applied. The flowsheet seen in
However, the use of TBP is restricted to the extraction from nitrate and Fig. 5 shows the separation process employed by the Kvenfjeld project in
chloride media (Gupta et al., 2002). Ordinarily, nitric acid is not Greenland. It is an example where two techniques are used to separate
preferred for leaching purposes except for nuclear waste treatment. thorium and uranium from the rare earth elements. As seen, while
Purification of impurities using TBP in kerosene also required multi- uranium is separated via solvent extraction, thorium is removed in the
stage extracting and stripping (Al-Areqi et al., 2015). Multiple con­ subsequent steps via hydrochloric acid leaching.
tacts between aqueous and organic solutions may increase the extraction Nonetheless, these separation processes may result in the loss of rare
efficiency; however, the organic extractant tends to be lost into the earths into impurity residues to a certain degree. For example, during
aqueous phase after a long contact between aqueous and organic phases. the impurity removal process of ion adsorbed clays, approximately 15%
For example, Saskatchewan Research Council has built a pilot-scale of rare earth elements may be lost to residues. In comparison, around 2%
processing plant that produces high purity (99%) rare earth via co- of it transferred to neutralization residues produced from acidic waste­
extraction of rare earths and uranium. The primary separation tech­ water. In that aspect, Su and his coworkers (2020) developed a cost-
nique is based on multi-stage solvent extraction, where around 150 effective process (Fig. 6) for recovering thorium and rare earth ele­
mixer-settlers are used. In a smaller laboratory scale, in Talan and ments from radioactive residue that those two were co-present.
Huang’s (2020) study, a two-stage solvent extraction process proved to Following the flowsheet, first, thorium separation via liquid–liquid
be more efficient than the single-stage process, during the former extraction is targeted, followed by the combination of extraction and
method of which approximately 97%, 94%, and 43% of rare earths, precipitation for further rare earth recovery. Another example of a
thorium, and uranium were recovered into the circuit rare earth product combined approach was given in an early Eco Ridge Mine project report.
stream, respectively. After co-extraction of uranium and rare earths during the preconcen­
Qi (2018) studied the extraction mechanism of thorium, uranium, tration steps, uranium is removed via solvent extraction using 2.5 v%
and rare earths in the TBP-HCl system and stated that the extraction Alamine and 2.5 v% Isodecanol mixture as the extractant. The

10
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Fig. 4. Separation of thorium and uranium by solvent extraction using TEHP (Biswas et al., 2013).

remaining solution is then treated with an organic mixture (i.e., 10% Before the development of solvent extraction, ion exchange was
D2EHPA and 2% TBP) and a stripping reagent (i.e., 1.5 N HNO3 mixed known as the most practical method to separate rare earths from im­
with 1.5 N H2SO4) to remove rare earth elements from the rest of the purities (Suli et al., 2017). It has also been used for fuel processing
impurities (i.e., thorium and iron). Lastly, the stripped solution is containing thorium and uranium (Chen et al., 2016). Even though the
neutralized with lime to a pH value of 3.2 to separate thorium and iron ion exchange application has been lessened, the need arises when the
that might come to the solution (Costis et al., 2021). loss of extractant into the aqueous phase or high impurity in the final
product is seen during the solvent extraction process. In addition, ion
3.3. Separation using Solid-Phase extraction techniques exchange requires fewer separation steps and consumes less chemical
reagents compared to solvent extraction (Ferrah et al., 2011).
Separation using solid materials is heavily used in metal separations, The resins used for the ion exchange are highly ionic reactive poly­
water and wastewater treatment, removal, and recovery of metal ions mers, covalently crosslinked, and classified based on the charge of the
(Sani et al., 2015). Ion exchange and adsorption processes are two very counter ion exchanger (Bertoli et al., 2019). Anion and cation resins are
similar solid–liquid separation techniques. However, adsorption can be the two most common types used in the ion-exchange process, which
explained by electrical attraction to the solid surface. In contrast, ion further divide into two subgroups, respectively, as strong base anionic,
exchange is defined as a process in which the chemical energy at equi­ strong acid cationic, and weak base anionic and weak acid cationic
librium after the process is lower than the initial (Jorgensen, 1989). resins. While anion resins attract negatively charged ions, cation resins
attract positively charged ions. A summary of the resin types and the
3.3.1. Ion exchange chemical structures is given in Table 10.
Ion exchange is a process in which ions are exchanged between a Several studies were conducted to remove radioactive elements from
solution and a solid (Hidayah and Abidin, 2017). The exchange reaction aqueous solutions by using various ion exchange resins (Song et al.,
between ions in solution and ions attached to the matrix is generally 1999; Vaaramaa et al., 2000; Merdivan et al., 2001; Chan­
reversible. The following reaction represents a fundamental exchange dramouleeswaran et al., 2011; Pulhani et al., 2012; Rahmati et al., 2012;
mechanism: Semnani et al., 2012; Chen et al., 2016; Qiu et al., 2017; Bertoli et al.,
2019). Ang and his coworkers (2017) performed a comprehensive study
A(solution) + B(solid)→A(solid) + B(solution) (16)
that examined the effectiveness of nine anionic and four cationic resins

11
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Fig. 5. Separation process employed by the Kvanefjeld project (Zhu et al., 2015).

on removing thorium and uranium from rare earth elements. Resin 1 finity towards rare earths was observed by Ang et al. (2017). The re­
was a primary amine weak-base anion exchanger within the nine searchers did not see any significant improvement in the adsorption
anionic exchangers, resin 2 and 3 were tertiary and quaternary amino recovery of uranium (nearly 30%) when the contact time was increased
groups containing intermediate-base anion exchanger, and resins 4 to 9 from 2 h to 24 h. On the contrary, the adsorption of rare earths (>95%)
were quaternary ammonium group containing strong-base anion ex­ and thorium (80%) were doubled when the contact time was increased.
changers. On the other hand, within the four cationic resins, two of them Uranium anionic species can explain the low uranium uptake in a
were sulfonic acid strong acid cation exchangers, and the other two were cationic resin environment. Contrarily, the high affinity of strong-base
carboxylic weak-acid cation exchangers. In Ang and his coworkers’ cationic resins toward rare earth element and thorium is because of
study, a synthetic solution containing 2 mmol/L of thorium, uranium, their higher metal charges. The best separation results were achieved
and rare earth elements in sulfate media was treated with various when the sulfuric acid concentration was between 0.05 and 0.1 mol/L
anionic exchangers for a total of 24 h contact time. The primary amine and the pH was between 0.07 and 1.
weak-base anion exchanger showed superior efficiency for thorium,
while an opposite behavior was observed for uranium. Uranium ex­ Th(NO3 )2−6 + 2P − NR3 X→(P − NR3 )2 Th(NO3 )6 + 2X − (17)
change recoveries were higher for the other types of anionic exchange
resins. The researchers concluded that rather than being weak or strong UO2 (SO4 )4−3 + 4P − NR3 X→(P − NR3 )4 UO2 (SO4 )3 + 4X − (18)
base anionic exchangers, the functional groups are more influential on Korkisch and Tera (1961), Gu et al. (2005), and Ladeira and Gon­
the results. Overall, the weak-base anionic resin resulted in the best calves (2007) performed ion exchange studies with strong-base anion
results with less than 5% rare earth co-exchange, while thorium and exchange resins, which are indicated as the most suitable resin type for
uranium separation was approximately 70% and 68% at pH 3 with thorium and uranium recovery, especially when they are recovered
0.0005 mol/L sulfuric acid. However, in another study, when the solu­ individually other than simultaneously. The effectiveness of this resin
tion medium is nitrate, thorium adsorption using strong base anionic type is exceptionally superior in sulfate and nitrate media (Judge and
resins have been reported to be more favorable (Judge and Azimi, Azimi, 2020). The strong-base anionic resins have quaternary amine
2020). The anion exchange of thorium from nitrate media is given in (NR3+) in their functional groups to make ion exchange happen. In Gu
reaction (17). Anion exchange of uranium from sulfate media is pro­ and his coworkers’ study, all six tested resins (i.e., A530E, A500, A520E,
vided in reaction (18), where X- represents the counter ion initially A850, Dowex 1-X8, WBR 109) showed good affinity towards uranium
loaded on the resin. with 8 to 24 h of retention time, regardless of the sulfate concentration
On the other hand, in the case of cationic exchangers, a higher af­

12
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Fig. 6. Process flowsheet developed for recovering thorium and rare earth elements from the radioactive residues of ion adsorbed rare earth ores (IREORR) (Su
et al., 2020).

uranium precipitation. This pH value also enhanced the uranium uptake

Table 10
since the accompanied iron ions precipitated as iron (III) hydroxide. The
Resin types, the functional groups, and their chemical structures (modified from
strong base anionic resins and strong acid cationic resins can be active at
Ang et al., 2017).
any pH level. However, weak acid cationic resins are more favorable due
Resin Type Functional Group Chemical to their opposite behavior and ability to release H+, which results in
Structure
higher ion exchange capacity than strong acid cation exchangers
Strong-base anionic ion Quaternary amine type 1 (Hidayah and Abidin, 2017), even though they act inactive in pH 4–6.
exchanger Quaternary amine type 2
Similarly, weak base anionic resins have limitations by working only at
Weak-base anionic ion exchanger Tertiary amine
Primary amine very low pH regions. Vaaramaa et al. (2000) conducted a study to
Strong-acid cationic ion Sulfonic acid compare strong-base anionic exchangers with aminophosphonate. It was
exchanger reported that at pH 5, aminophosphonate resin worked better than
Weak-acid cationic ion exchanger Carboxylic acid strong-base anionic resin; however, due to the presence of UO2(SO4)3-4
type of ions, the use of strong-base anionic resins are more favorable
of the solution. However, the researchers stated that Purolite A850 has when acidic water feedstock is used.
the highest affinity for uranium while Dowex 1-X8 and Purolite A500 Ion exchange is a selective process, which means the ions attached to
have the lowest affinity. The reason for relatively different adsorption the matrix will prefer one counter ion over another. For instance,
between the resins can be due to the differences in their exchange sites. Semnani et al. (2012) observed that the affinity of uranium onto
For example, while WBR109 has smaller tributyl ammonium exchange Amberlite CG-400 resin decreases when the phosphate anions in the
sites, A530E has larger tri hexyl ammonium sites, and DOWEX 1-X8 and solution increase since phosphate anions will compete with uranium
A500 both have tri methyl ammonium functional groups. In general, the anions. The formation of phosphate anions is due to the rise in pH, which
adsorption rate increases as the length of tri alkyl ammonium functional is a vital parameter for a successful ion exchange process. Ang and his
groups decreases. However, the researchers stated the ineffectiveness of coworkers (2017) observed a similar competing behavior between
the resins studied at high pH values. When the pH exceeds typically 4, uranium and sulfate ions. Sulfuric acid concentration of the medium was
hydrolysis of other ions is noticed, which may be sorbed by the resins stated as an influential parameter when ion exchangeability was
and reduce the separation efficiency. Moreover, precipitation of the ions investigated, and a suppressing effect of sulfate ions was observed.
of interest may happen at higher pH values, decreasing the separation Effective uranium separation was achieved when the sulfuric acid con­
performance. For example, in Korkisch and Tera’s study (1961), it was centration was 0.1 mol/L or lower and the solution pH was > 0.7. Cheira
stated that the uptake of lanthanides could be eliminated by keeping the et al. (2017) also studied uranium separation from a sulfate leach liquor
pH at 4.5 and preventing the hydrolysis of lanthanides. On the contrary, by an anionic exchange resin, Ambersep 920U SO4. The researchers first
Gu and his coworkers’ study was conducted at pH 8.5, resulting in high observed an increase in the uranium adsorption as pH increased from 1
uranium removal. to 2. It reached a maximum at pH 2–3.5, which then started to decrease
On the other hand, Ladeira and Goncalves (2007) studied uranium between pH 3.5 and 5 due to the formation of precipitates. Higher
removal from acid mine water at a maximum pH value of 3.9 to prevent adsorption recoveries were also obtained as contact time and adsorbent
amount were gradually increased from 10 to 120 mins and 25 to 200 mg,

13
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

respectively. As a result, 99% of uranium adsorption was generated Similarly, Reynier et al. (2021) investigated the selectivity of several
using 200 mg of Ambersep 920U SO4 at pH 2 with a contact time of 120 resin types, including the chelating and impregnated resins, on the re­
mins. covery of thorium, uranium, and rare earth elements from a bio-leached
Sometimes, more than one technique is used to enhance separation uranium tailing sample. Among the five chelating resins with different
efficiency. For example, Papadopoulos et al. (2004) applied both pre­ functional groups (i.e., thiol, thiourea, bis-picolylamine, aminomethyl
cipitation and ion exchange techniques to increase the removal rate by phosphonic, iminodiacetate), Lewatit TP260 with aminomethyl phos­
20% compared to a single technique. Another group of researchers also phonic functional group resulted in better separation between thorium,
applied a combined approach to selectively separate uranium and rare uranium, and rare earth elements. The respective recovery values were
earth elements (Hamza et al., 2019). Their study first used selective reported as 55%, 93%, and 30%, respectively. Among the tested
precipitation to separate impurities; then, the solution was treated with impregnated resins, D2EHPA-impregnated Lewatit VPOC 026 resulted
a magnetic resin to separate uranium from rare earth elements. A high in enhanced separation than trimethyl pentyl-phosphinic-impregnated
enrichment factor was achieved, and the final residue was uranium- Lewatit TP 272 resin. The former produced 69% of thorium, 71% of
depleted. Nonetheless, due to the limitations of the ion exchange feed uranium, and approximately 20% of rare earth removal. However, both
flow rate, the application of liquid–liquid extraction processes is chelating and D2EHPA impregnated resins co-recovered a substantial
preferred from the standpoint of potential scale-up (Garcia et al., 2020). amount of scandium, >65%. Qui et al. (2017) studied ODP impregnated
Moreover, it is a highly complicated phenomenon that depends signifi­ resin to remove thorium and uranium from rare earth elements. 64% of
cantly on the nature of the materials and the aqueous chemistry of the thorium separation was achieved with ODP impregnated resin in nitrate
system. media while rare earth and impurity elements (such as iron) co-
Another group of ion exchangers is chelating and solvent- extraction were minimal. The separation efficiency of thorium was
impregnated resins. Chelating resins were developed to overcome the increased to an even higher value of 95% when D2EHPA impregnated
limitations in traditional cationic and anionic ion exchangers. They resin was used, and uranium separation efficiency was around 80%.
exhibit higher selectivity than the conventional resins since they can
undergo surface modifications, thus, making themselves more selective 3.3.2. Adsorption
to the ions of interest. Impregnated resins, on the other hand, are Nowadays, the application of adsorption using porous solid sorbent
accepted as an alternative to solvent extraction systems, and they are has been gradually increased due to its high efficiency, easy handling,
simply produced by reacting a solvent with insoluble support (resins). low maintenance, and operating costs over other techniques (Liu et al.,
The solvent is contacted with the resin, which soaks the extractant rather 2013; Nandanwar et al., 2016). It has advantages over conventionally
than forming bonding. Page et al. (2017) studied several chelating used solvent extraction by eliminating the consumption of organic
resins, including mixed sulfonic/phosphonic, aminophosphonic, and extractants and reducing environmental pollution that organic chem­
iminodiacetic acid functional groups, to observe their ability to separate icals may create (Xiong et al., 2020). Adsorption has also been used for
individual rare earths; however, the study indicated no significant af­ fuel processing, containing thorium and uranium (Chen et al., 2016).
finity towards rare earths. Instead, it was concluded that these chelating Sorbents are available in various forms, such as natural and synthetic
resins could be applied to remove impurity elements, such as iron, organic, inorganic, or composite materials. Their surfaces are often
thorium, and uranium. Ang et al. (2018) performed a detailed study heterogeneous, and bonding energies may vary from one site to another.
where five chelating and two impregnated resins were evaluated based Materials like zeolite, apatite, activated carbon, calcined phosphate,
on their performance of removing uranium and thorium from rare earth oxides, and hydroxides are examples of some highly abundant sorbents
elements in sulfate medium. Within the five tested chelating resins, the (Ladeira and Goncalves, 2007). Especially silica-based materials have
one with the bis-picolylamine group showed relatively higher affinity suitable physical, chemical, and thermal stability. There are plenty of
for uranium in 0.05 mol/L sulfuric acid at 2 h contact time. While the studies about thorium and uranium adsorption on different materials
adsorption recovery of uranium was 44%, the recovery of rare earth (Aksoyoglu, 1989; Badei et al., 1992; Milonjic et al., 1992; Qadeer et al.,
elements and thorium under the same conditions was 10% and 16%, 1992; Jain et al., 2001; Kilislioglu and Bilgin, 2003; Humelnicu et al.,
separately. The uranium adsorption increased to 89% when the contact 2006; Sikalidis et al., 2008; Wang et al., 2012; Liu et al., 2013; Kaynar
time was increased to 24 h while keeping the acidity constant. However, et al., 2015). The adsorption mechanism starts with a complex formation
this new operating condition observed no difference in the adsorption of directly with the adsorbent surface, which lies on the Stern Layer. As the
thorium or rare earths. For simultaneous separation of thorium and valence of a cation increases, the tendency of complexation also in­
uranium, iminodiacetic chelating resins yielded better performance. creases. Later the cation creates an outer-sphere complex, in which at
With 24 h contact time and 0.05 mol/L solution acidity, adsorption of least one water molecule is in between the cation and the adsorbent.
uranium and thorium were around 70% and 60%, respectively. The rare Sometimes, the cation, which is surrounded by water molecules, may
earth adsorption under the same conditions was less than 8%. However, locally neutralize the surface charge of the adsorbent instead of forming
based on the tested acidity range (i.e., 0.0005 to 2 mol/L), feasible a complex. In that case, the ion lies in the diffusion layer. While the
separation of thorium and uranium from rare earths was achieved when complexes on the Stern layer may have covalent or ionic bonding, the
the solution acidity was 0.1 mol/L or lower, and the best separation ions in the diffusion layer only have ionic bonds. Following adsorption,
performance was achieved when the solution medium was 0.005 mol/L desorption is performed by either elevating the temperature, reducing
sulfuric acid and at pH 2. Under these operating conditions, uranium the pressure, or washing with a suitable reagent. The desorbed material
and thorium adsorption was around 90%, while rare earth adsorption may be recovered as a valuable product or discarded as waste (Couper
was below 30%. Nevertheless, no separation was observed between the et al., 2009).
elements when chelating resins containing the aminophosphonic func­ The adsorption process depends on the chemical nature of both fluid
tional group were used regardless of the contact time. On the other hand, and solid. Also, it is highly affected by the available surface area and
between the explored impregnated resins, the highest uranium adsorp­ pore volume of the adsorbent. Besides, the selectivity depends on many
tion recovery of 93% was achieved with a bis-(2,4,4-trimethylpentyl) other factors such as the particle size of the absorbent, pH of the solu­
phosphinic acid impregnated resin (0.05 mol/L H2SO4, 2-hour contact). tion, contact time, nature of the solution, etc. The pH plays an essential
Although commonly used in commercial solvent extraction units, role in sorption processes because it can influence the aqueous chemistry
D2EHPA impregnated resin did not yield high adsorption. The of the ions determining the hydrolysis products and the properties of the
maximum uranium adsorption was 65% generated at the end of 24 h active sites of the sorbent (Faghihian et al., 2004; Cheira et al., 2017). It
contact time. The thorium removal was around 45%, and the rare earth also affects the external charge of the adsorbent, which results in a
adsorption recovery was around 15% under the same testing conditions. change in the electrostatic interactions. It was seen that the capacity of

14
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

uranium adsorption increases with increasing pH and reaches a values (1 to 2.8). The adsorption mechanism was determined as pseudo-
maximum value at a pH range of 2.0 to 3.5 (Cheira et al., 2017). Another second-order chemical adsorption. Hunter et al. (1988) studied thorium
report published by the U.S. Environmental Protection Agency (1999) uptake by goethite and nsutite (ɤ-MnO2) and observed the formation of
stated that when carbonate ions are present, the adsorption of uranium competitive complexes. In their study, as the concentration of sulfate
reaches its maximum in the pH range of 5 to 8 and decreases as the pH ions increases, the adsorption of thorium decreases due to the compe­
continues to increase. Osthols’ (1995) study on adsorption of thorium tition between the two ions.
onto amorphous colloidal silica particles indicated that the most effi­ As another group of sorbents, microorganisms are frequently studied.
cient pH range is between 3 and 6. As pH reaches neutral and alkaline The use of microorganisms is the cheapest and most environmentally
values, it was observed that the silica sites are not adsorbing thorium friendly route of ion adsorption. Bacillus subtilis, Escherichia coli, Pseu­
sufficiently anymore. In general, due to the formation of hydrolysis domonas fluorescens, Paracoccus denitrificans, Schwanella putrefaciens,
products, the adsorption of thorium and uranium onto various adsor­ and Alcaligenes faecalis are the most common microorganisms (Hidayah
bents is kept below pH 5 (Sikalidis et al., 2008). Particle size distribution and Abidin, 2017). For example, Bacillus subtilis tends to separate heavy
is another critical factor due to its influence on the pressure loss upon rare earth elements in which the absorption is fast (around 10 mins) and
passing the solvent through the sorbent. It also affects mass transfer at a relatively low pH level (i.e., 4). Although higher bacteria concen­
rates. Pressure loss increases with decreasing particle size, and mass tration seems favorable, a further increase in pH causes degradation and
exchange rates also increase with decreasing particle size because of reduces the separation performance. Tsezos and Volesky (1982) studied
shorter diffusion paths (Kammerer et al., 2011; Monji et al., 2016). An thorium uptake by a different microorganism, Rhizopus Arrhizus, and
increase in adsorption capacity is expected when the particles are finer observed optimum thorium biosorption at pH 4 by a rapid process.
since the effective surface area increases as the size decreases (Zou et al., Bhainsa and D’Souza, (2001) and Nakajima and Tsuruta (2004) investi­
2009). The pore size distribution also plays a significant role in the gated uranium uptake on Systoseira Indica and reported similar results.
diffusion of the solutes onto the sorbents. Compounds with an ampho­ Maximum adsorption was achieved in both studies at pH 4, around
teric nature obtain the maximum adsorption at the isoelectric point 25–30 ◦ C, with a retention time of 3 h. Similarly, an engineered bacteria
(Jorgensen, 1989). was used by Bonificio and Clarke (2016). Nonetheless, the use of micro­
In the early years, Doi et al. (1975) conducted a comprehensive study organisms is effective on a small scale; their application on an industrial
about uranium adsorption on a wide variety of sorbents such as peat, scale was stated as uneconomical (Hidayah and Abidin, 2017).
ferric oxide, clay minerals, zeolite, calcite, and apatite. The highest Sometimes the sorbent needs surface modification to enhance its
uranium uptake on peat was observed at a pH range of 3.8–8.5. It was adsorption capability. The modified material is called synthetic sorbent,
noticed that the humic acid in the peat was causing uranium adsorption. which is more stable compared to its natural form (Ullah et al., 2012).
As the coalification progressed, uranium adsorption decreased in the Uranium removal by manganese oxide-coated and iron oxide-coated
order of peat, lignite, bituminous coal, and anthracite. The same re­ zeolite samples were studied extensively by multiple researchers (Han
searchers also studied adsorption by calcite and apatite, which resulted et al., 2007; Zou et al., 2009; Nekhunguni et al., 2017). Iron and man­
in a positive correlation between adsorption and the amount of sorbent ganese oxides are expected to be more effective than other adsorbents.
used. Khalili and Al-Banna (2015) studied thorium and uranium Generally, an increase in the adsorption capacity was observed with an
adsorption by humic acid. They stated that adsorption by humic sub­ increased pH until 6 and adsorbent amount. However, compared to
stances is achieved via forming complexes with carboxylic and other clinoptilolite type zeolite, magnetite nanoparticles, and titanium oxide
acidic functional groups by replacing hydrogen ions with the ions of modified clays, the adsorption capacity of iron oxide-coated zeolite
interest. Fasfous and Dawoud (2012) performed a thorough study on samples was significantly lower in Nekhunguni and his coworkers’
uranium adsorption by multi-walled carbon nanotubes (CNT). The re­ (2017) study. In another study by Wang et al. (2013), a synthesized
searchers also examined the kinetic and thermodynamic aspects of the mesoporous material named SBA-15 was used to remove uranium in a
adsorption process. CNT is more favorable among carbon-based mate­ nitrate medium. Consistent with previously mentioned studies, this
rials (i.e., carbon nanotubes, graphene, carbon fibers) due to its high study also reported increased uranium adsorption with an elevated pH.
specific surface area (Yadav et al., 2019). Alternatively, Kutahyali and However, after pH 6, the uranium adsorption slowed down and dimin­
Eral (2010) investigated the adsorption of thorium and uranium on ished due to the dissolved carbonate and bicarbonate ions, which
activated carbon. In a similar study performed with activated carbon, compete with the uranium ions for available adsorption sites. The study
Yakout (2017) stated that uranium adsorption on KOH-modified acti­ achieved 79% uranium adsorption with the synthesized adsorbent in 30
vated carbon is more selective than thorium adsorption. In contrast, min of equilibrium time at pH 6. Kinetic adsorption studies suggested
thorium uptake is higher on nitric acid-modified activated carbon. Monji Langmuir isotherm and pseudo-second-order rate for the studied system.
et al. (2016) and Youssef et al. (2018) studied the adsorption of uranium On the other hand, Metaxas et al. (2003) focused on thorium
ions in the presence of lanthanides using a byproduct of the agricultural adsorption using different zeolite samples in addition to investigating
industry. Considering the immense quantities of agricultural waste, their the effect of the modified (pretreated) samples. Metaxas and his co­
use for the adsorption of ions substantially benefits the environment. workers’ study (2003) showed that NaCl-treated synthetic zeolites had
Among the seven different agricultural waste types, Monji et al. reported higher removal efficiency than natural zeolite samples. The reason for
that rice bran has higher selectivity for uranium in 4 mol/L hydrochloric higher removal with synthetic zeolites is their larger framework chan­
acid when lanthanides are present. On the contrary, pine tree sawdust, nels and their higher number of active exchange sites. On the other
tea factory waste, wheat bran, rice hull, orange peel, and lemon peel hand, compared to clinoptilolite type zeolite, mordenite type zeolite was
were found to be less effective due to competition between hydrogen more efficient. While the thorium removal with Na-mordenite was 0.64
and uranium ions at the binding sites. meq/g, it was significantly lower (0.25 meq/g) with Na-clinoptilolite.
Most recently, Xiong et al. (2020) studied membrane-based separa­ Higher thorium uptake was also observed with NaCl-treated zeolite in
tion using a novel sorbent (covalent organic frameworks, i.e., COFs). nitrate media in an earlier study conducted by Misaelides et al. (1995).
Separation via membranes is achieved by forming a complex between Although in their research, uranium uptake was not enhanced when a
the element of interest and the membrane. Adsorption via membrane is pretreated zeolite sample was used. Baybas and Ulusoy (2011) used
efficient in acidic conditions and at pH values between 4 and 5.5. Be­ composites prepared from polyacrylamide (PAAm) and aluminosilicates
sides, it consumes less energy, is easy to operate, and has an increased for thorium uptake to eliminate the limiting features of aluminosilicates
diffusion rate, resulting in enhanced high-speed adsorption (Xu et al., alone, which may be occurring due to aggregation and coagulation in
2009; Garcia et al., 2020). In Xiong and his coworkers’ study, high and the system. Using a polymer, the diffusion of the ions towards the
fast adsorption capacities for thorium were observed at all tested pH mineral can be enabled due to the swelling capability of the polymer in

15
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

the aquatic environment; thus, the adsorption process may be signifi­ via precipitation, solvent extraction, and solid-phase extraction due to
cantly enhanced. As a result, higher adsorption onto the composites of their wide applications in the field.
PAAm-Montmorillonite, PAAm-Clinoptilolite, and PAAm-Zeolite was Among the techniques reviewed, selective precipitation is easier to
seen compared to aluminosilicates alone. In addition, modification of operate and less costly; however, a second approach is almost always
the samples with phytic acid generated even better results than the needed to reduce the radionuclide content further. Typically, a combina­
composites alone. Nearly 100% thorium adsorption was achieved with tion of multiple separation techniques is more effective. Solvent extraction
phytic acid-treated PAAm-clinoptilolite composite. The pH change re­ is the most effective and preferred technique with proven commercial-scale
sults in protonation or deprotonation in the structure of aluminosilicates operations. Various extractant types can be used to separate thorium and
(Reactions. (19) and (20)), causes surface charge and affects overall uranium in the presence of rare earth-containing solutions under
adsorption efficiency. controlled operating conditions. In general, tertiary amines are preferred
for uranium separation, while primary amines are more selective towards
≡ SOH + H + → ≡ SOH + (19)
2 thorium. However, the use of other types of extractants has also been
studied frequently. Ion exchange is used to produce high purity rare earth
≡ SOH→SO− + H + (20)
products, which also has applications in fuel processing. Although the
Even though several studies were performed to examine the possible application on a large scale is limited, radionuclide uptake on sorbents with
application of sorbents to remove naturally occurring heavy metals and different forms (e.g., microorganisms, an agricultural byproduct, minerals,
radioactive materials, these studies were primarily performed for etc.) is an alternative and promising method, with an advantage over sol­
decontamination of polluted waters rather than rare earth production. vent extraction by eliminating the use of a chemical reagent. While some
Within that context, Talan and Huang (2021) investigated the removal studies showed a separation challenge between rare earth elements and
of thorium and uranium from rare earth elements-containing solutions uranium due to their similar adsorption behaviors, other studies achieved
generated from coarse coal refuse by zeolite adsorption. The best sepa­ high adsorption recoveries using pretreated adsorbents. The application of
ration performance was achieved while using 2.50 g of 12-µm zeolite agricultural byproducts or microorganisms also increases; however, the
sample at a pH value of 3 with a contact period of 2 h. Under these process is primarily applicable to passive treatment or rare earth recovery
conditions, the adsorption recovery of rare earths, thorium, and ura­ from acid mine drainage. Their application in a mining purification process
nium into the solid phase was found to be 20.43 wt%, 99.20 wt%, and needs to be further investigated.
89.60 wt%, respectively. Uranium adsorption onto zeolite studied by
Kilincarslan and Akyil (2005) suggests similar results concerning con­ Declaration of Competing Interest
tact time. 120 min of contact was identified to be sufficient within the
studied range (5–420 mins). Although there are numerous studies on The authors declare that they have no known competing financial
adsorption, it has its disadvantages, such as low selectivity, low loading interests or personal relationships that could have appeared to influence
capacity, complex adsorption behavior, etc. In fact, in Talan and the work reported in this paper.
Huang’s (2021) study, it was reported that rare earths and uranium
adsorption follow a similar pattern, which creates the separation chal­ References
lenge. The reason for this phenomenon can be the competition between
rare earth and uranium ions. As opposed to rare earth elements and Abdel-Razek, Y., Desouky, O., Elshenawy, A., Nasr, A., Mohammed, H., Elsayed, A.,
2016. Assessment of the Radiation Exposures During Separation of Rare Earth
uranium, test results indicate that zeolite adsorption is an effective Elements from Monazite Mineral. Int. J. Adv. Res. 265–272.
technique for thorium removal. Another explanation for low selectivity Abdel-Sabour, M. (2014). Uranium Fixation and Removal from Different Soil Types:
towards uranium can be calcium, magnesium, and potassium ions pre­ Review. Journal of Nuclear Energy Science and Power Generation Technology.
Adeel, M., Lee, J., Zain, M., Rizwan, M., Nawab, A., Ahmad, M., Xing, B., 2019. Cryptic
sent in the solution. Depending on the ionic strength of the solutions,
Footprints of Rare Earth Elements on Natural Resources and Living Organisms.
these cations may cause a displacement, forcing uranium ions into the Environ. Int. 785–800.
solution (U.S. EPA,1999). Akdogan, G., & Ghosh, T. (2014). Identification of REE in Some Alaskan Coal and Ash
Samples. Mineral Industry Research Laboratory (MIRL) Institute of Northern
Engineering, University of Alaska Fairbanks.
4. Summary and conclusions Akkaya, R., 2013. Uranium and Thorium Adsorption from Aqueous Solution Using A
Novel Polyhydroxyethylmethacrylate-pumice Composite. J. Environ. Radioact.
58–63.
Among all other critical raw materials, rare earths occupy a vast
Aksoyoglu, S., 1989. Sorption of U(VI) on Granite. J. Radioanal. Nucl. Chem. 393–403.
portion. The challenge to meet the demand for rare earth elements will Al-Areqi, W., Aniza, C., Bahri, C., Majid, A., Sarmani, S., 2016. Separation and
continue rising in the long run, in line with the advancements in fast Radiological Impact Assessment of Thorium in Malaysian Monazite Processing.
emerging green technologies and high-tech devices. In that regard, Malaysian J. Analyt. Sci. 770–776.
Al-Areqi, W., Majid, A., Sarmani, S., 2014. Thorium, uranium and rare earth elements
sustainable processing and recycling schemes have presented significant content in lanthanide concentrate (LC) and water leach purification (WLP) residue of
opportunities that align with today’s environmental regulations. This lynas advanced materials plant (LAMP). American Institute of Physics Conference
study provided a brief overview of recent advances in rare earth Proceedings 93–96.
Al-Areqi, W., Majid, A., Sarmani, S., Bahri, C., 2015. Thorium: Issues and Prospects in
resource exploration activities. Malaysia. AIP Conference Proceedings. American Institute of Physics, p. 1659.
On the other hand, the environmental prospect of rare earth mining Alex, P., Suri, A., Gupta, C., 1998. Processing of Xenotime Concentrate. Hydrometallurgy
needs to be thoroughly considered. Radiation caused by rare earth 331–338.
Amaral, J., Morais, C., 2010. Thorium and Uranium Extraction from Rare Earth Elements
mining activities raises severe concerns for both the public and the in Monazite Sulfuric Acid Liquor Through Solvent Extraction. Miner. Eng. 498–503.
surroundings, and unfortunately, there is not sufficient information on Amato, A., Becci, A., Birloaga, I., De Michelis, I., Ferella, F., Innocenzi, V., Beolchini, F.,
this subject. While focusing on the technical feasibility and economic 2019. Sustainability Analysis of Innovative Technologies for the Rare Earth Elements
Recovery. Renew. Sustain. Energy Rev. 41–53.
viability of the rare earth element extraction from conventional and Amer, T., Abdeall, W., Abdel Wahab, G., El-Sheikh, E., 2013. A Suggested Alternative
unconventional sources, ensuring that the process is environmentally Procedure for Processing of Monazite Mineral Concentrate. Int. J. Miner. Process.
acceptable is equally crucial. Even though the average concentrations of 106–111.
Anderson, C., Taylor, P., Anderson, C., 2017. Rare Earth Flotation Fundamentals: A
radioactive matter are lower in the secondary sources than those of the
Review. American J. Eng. Res. 155–166.
primary sources, it still requires special consideration since their con­ Ang, K., Li, D., Nikoloski, A., 2017. The Effectiveness of Ion Exchange Resins in
centrations may be increased along with the processing scheme. This Separating Uranium and Thorium from Rare Earth Elements in Acidic Aqueous
study provided a detailed review of the environmental aspect of rare Sulfate Media Part 1. Anionic and Cationic Resins. Hydrometallurgy 147–155.
Ang, K., Li, D., Nikoloski, A., 2018. The Effectiveness of Ion Exchange Resins in
earth mining and potential separation/remediation techniques for Separating Uranium and Thorium from Rare Earth Elements in Acidic Aqueous
thorium and uranium removal, with the major focus being on separation Sulfate Media. Part 2. Chelating Resins. Miner. Eng. 8–15.

16
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Anon, 2012. Rare Earth Elements: A Review of Production, Processing, Recycling and Elshkaki, A., Graedel, T., 2014. Dysprosium, the Balance Problem, and Wind Power
Associated Environmental Issues. United States Environmental Protection Agency: Technology. Appl. Energy 548–559.
EPA/600/R-12/572. Eskanazy, G., 1987. Rare Earth Elements and Yttrium in Lithotypes of Bulgarian Coals.
Asselin, G., Audrieth, L., & Comings, E., 1949. The Separation of Thorium and Rare Erath Org Geochem. 83–89.
Salts by Solvent Extraction. 640-648. Eskanlou, A., Huang, Q., 2021. Phosphatic waste clay: Origin, composition,
Ault, T., Krahn, S., Croff, A., 2015. Radiological Impacts and Regulations of Rare Earth physicochemical properties, challenges, values and possible remedies–A review.
Elements in Non-Nuclear Energy Production. Energies 2066–2081. Miner. Eng. 162, 106745.
Aziman, E., Ismail, A., 2020. Frontier Looking of Rare-Earth Processed Residue As Faghihian, H., Maragheh, M., Amini, M., Nezamzadeh, A., 2004. Adsorption Science and
Sustainable Thorium Resources: An Insight into Chemical Composition and Technology. Thorium Ion Uptake by Zeolite A Synthesized from Natural.
Separation of Thorium. Prog. Nucl. Energy 103471. Clinoptilolite Tuffs. 707–717.
Badei, M., El-Naggar, I., El-Belihi, A., Aly, H., Aly, H., 1992. Sorption Behaviour of Fasfous, I., Dawoud, J., 2012. Uranium(VI) Sorption by Multiwalled Carbon Nanotubes
Uranium on Tin(IV) Antimonate from Aqueous Solutions. Radiochim. Acta 89–92. from Aqueous Solution. Appl. Surf. Sci. 433–440.
Balaram, V., 2019. Rare Earth Elements: A Review of Applications, Occurrence, Ferrah, N., Abderrahim, O., Didi, M., Villemin, D., 2011. Sorption Efficiency of A New
Exploration, Analysis, Recycling, and Environmental Impact. Geosci. Front. Sorbent Towards Uranyl: Phosphonic Acid Grafted Merrifield Resin. J. Radioanal.
1285–1303. Nucl. Chem. 721–730.
Barakos, G., Mischo, H., & Gutzmer, J., 2014. Assessment of Boundary Conditions and Findeiß, M. (2016). Effects of Radioactive By-products Along with the Extraction of Rare
Requirements for Rare Earth Underground Mining Due to Presence of NORMS. Earth Elements on Aquatic and Terrestrial Organisms. Aachen: Thesis.
ERES2014: 1st European Rare Earth Resources Conference , (pp. 133-139). Milos. FindeiB, M., Schaffer, A., 2017. Fate and Environmental Impact of Thorium Residues
Baybas, D., Ulusoy, U., 2011. The Use of Polyacrylamide-Aluminosilicate Composites for During Rare Earth Processing. J. Sustain. Metall. 179–189.
Thorium Adsorption. Appl. Clay Sci. 138–146. Finkelman, R., 1999. Trace Elements in Coal Environmental and Health Significance.
Belova, V., Egorova, N., Voshkin, A., Khol’kin, A., 2015. Extraction of Rare Earth Metals, Biol. Trace Elem. Res. 197–204.
Uranium and Thorium from Nitrate Solutions by Binary Extractants. Theor. Found. Finkelman, R., Palmer, C., Wang, P., 2018. Quantification of the Modes of Occurrence of
Chem. Eng. 545–549. 42 Elements in Coal. Int. J. Coal Geol. 138–160.
Bertoli, A., Quintao, M., De Abreu, H., Ladeira, A., Duarte, H., 2019. Uranium Separation Flett, D., 1992. Solution Purification. Hydrometallurgy 327–344.
from Acid Mine Drainage Using Anionic Resins - An Experimental/Theoretical Fouquet, Y., & Martel-Jantin, B., 2014. Rare and Strategic Metals. In Y. Fouquet, & D.
Investigation of Its Chemical Speciation and the Interaction Mechanism. Journal of Lacroix, Deep Marine Mineral Resources (pp. 55-64). Springer.
Environmental. Chem. Eng. Garcia, A., Latifi, M., Amini, A., & Chaouki, J., 2020. Separation of Radioactive Elements
Bhainsa, K., D’Souza, S., 2001. Uranium (VI) Biosorption by Dried Roots of Eichhornia from Rare Earth Element-Bearing Minerals. Metals, 1524.
Crassipes (Water Hyacint). J. Environ. Sci. Healt - Part A Toxic/Hazardous Subst. Garcia-Tenorio, R., Manjon, G., Vioque, I., Jimenez-Ramos, M., Mantero, J., Diaz-
Environ. Eng. 1621–1631. Frances, I., 2018. Grey Monazite (Rare Earths) Mining in Centre of Spain:
Binnemans, K., Jones, P., 2015. Rare Earths and the Balance Problem. J. Sustain. Metall. Characterization and Pre-operational Radiological Evaluation. Chemosphere
29–38. 691–697.
Biswas, S., Pathak, P., Singh, D., Roy, S., 2013. Comparative Evaluation of Tri-n-butyl Giri, R., Nath, G., 2016. Physicochemical Study of Extractants for Extraction of Rare
Phosphate (TBP) and Tris(-ethylhexly) Phosphate (TEHP) for the Recovery of Earth Element. J. Anal. Sci. Technol.
Uranium from Monazite Leach Solution. Sep. Sci. Technol. 2013–2019. Gu, B., Ku, Y., Brown, G., 2005. Sorption and Desorption of Perchlorate and U(VI) by
Blissett, R., Smalley, N., Rowson, N., 2014. An Investigation into Six Coal Fly Ashes from Strong-Base Anion-Exchange Resins. Environ. Sci. Technol. 901–907.
the United Kingdom and Poland to Evaluate Rare Earth Element Content. Fuel Guyonnet, D., Planchon, M., Rollat, A., Escalon, V., Tuduri, J., Charles, N., Fargier, H.,
236–239. 2015. Material Flow Analysis Applied to Rare Earth Elements in Europe. J. Cleaner
Bonificio, W., Clarke, D., 2016. Rare-Eath Separation Using Bacteria. Environ. Sci. Prod. 215–228.
Technol. Lett. 180–184. Gupta, B., Malik, P., Deep, A., 2002. Extraction of Uranium, Thorium and Lanthanides
Borai, E., Shahr El-Din, A., El-Sofany, E., Sakr, A., El-Sayed, G., 2014. Extraction and using Cyanex 923: Their Separations and Recovery from Monazite. J. Radioanal.
Separation of Some Naturally Occurring Radionuclides from Rare Earth Elements by Nucl. Chem. 451–456.
Different Amines. Arab J. Nucl. Sci. Appl. 48–60. Hamza, M., El-Aassy, I., Guibal, E., 2019. Integrated Treatment of Tailing Material for the
British Geological Survey. (2011). Rare Earth Elements. Selective Recovery of Uranium, Rare Earth Elements and Heavy Metals. Miner. Eng.
Brown, C., Sherrington, L., 1979. Solvent Extraction used in Industrial Separation of Rare 138–148.
Earths. J. Chem. Technol. Biotechnol. 193–209. Han, R., Zou, W., Wang, Y., Zhu, L., 2007. Removal of Uranium(VI) from Aqueous
Camacho, L., Deng, S., Parra, R., 2010. Uranium Removal from Groundwater by Natural Solutions by Manganese Oxide Coated Zeolite: Discussion of Adsorption Isotherms
Clinoptilolite Zeolite: Effects of pH and Initial Feed Concentration. J. Hazard. Mater. and pH Effect. J. Environ. Radioact. 127–143.
393–398. Haridasan, P. (2013). Managing Exposure to Natural Sources: International Standards
Chandramouleeswaran, S., Ramkumar, J., Sudarsan, V., Reddy, A., 2011. and New Challenges. Proceedings of the Seventh Naturally Occurring Radioactive
Boroaluminosilicate Glasses: Novel sorbents for Separation of Th and U. J. Hazard. Material (NORM VII) (pp. 31-48). Beijing: IAEA, Vienna.
Mater. 159–164. He, Y., 2014. Regulations of China’s Rare Earth Production and Export. Int. J. Emerg.
Charalampides, G., Vatalis, K., Apostoplos, B., Nikolas, B., 2015. Rare Earth Elements: Markets 236–256.
Industrial Applications and Economic Dependency of Europe. Procedia Economics Hedrick, J. (2000). Thorium. U.S. Geological Survey Minerals Yearbook.
Finance 126–135. Hidayah, N., Abidin, S., 2017. The Evolution of Mineral Processing in Extraction of Rare
Cheira, M., Atia, B., Kouraim, M., 2017. Uranium (VI) Recovery from Acidic Leach Liquor Earth Elements Using Solid-Liquid Extraction over Liquid-Liquid Extraction - A
by Ambersep 920U SO4 Resin: Kinetic, Equilibrium and Thermodynamic Studies. Review. Miner. Eng. 103–113.
J. Radiat. Res. Appl. Sci. 307–319. Hoenderdaal, S., Espinoza, L., Marscheider-Weidemann, F., Graus, W., 2013. Can A
Chellam, S., Clifford, D., 2002. Physical-Chemical Treatment of Groundwater Dysprosium Shortage Threaten Green Energy Technologies? Energy 344–355.
Contaminated by Leachate from Surface Disposal of Uranium Tailings. J. Environ. Holden, C., & Burchfield , L. (2010). U.S. Patent No. US20100018347A1.
Eng. 942–952. Honaker, R., Groppo, J., Bhagavatula, A., Razaee, M., Zhang, W., 2016. Recovery of Rare
Chen, Y., Wei, Y., He, L., Tang, F., 2016. Separation of Thorium and Uranium in Nitric Earth Minerals and Elements from Coal and Coal Byproducts. Louisville, KY.
Acid Solution Using Silica Based Anion Exchange Resin. J. Chromatogr. A 37–41. Honaker, R., Zhang, W., Werner, J., 2019. Acid Leaching of Rare Earth Elements from
Chu, S., 2011. Critical Materials Strategy. DIANE Publishing. Coal and Coal Ash: Implications for Using Fluidized Bed Combustion to Assist in the
Cooper, M., 2005. Naturally Occurring Radioactive Materials (NORM) in Australian Recovery of Critical Materials. Energy Fuels 5971–5980.
Industries - Review of Current Inventories and Future Generation. Radiation Health Hostetler, P., Garrels, R., 1962. Transportation and Precipitation of Uranium and
and Safety Advisor Council. Vanadium at Low Temperatures with Special Reference to Sandstone-Type Uranium
Costis, S., Mueller, K., Coudert, L., Neculita, C., Reynier, N., Blais, J., 2021. Recovery Deposits. Econ. Geol. Bull. Soc. Econ. Geol. 137–167.
Potential of Rare Earth Elements from Mining and Industrial Residues: A Review and Hower, J., Granite, E., Mayfield, D., Lewis, A., Finkelman, R., 2016. Notes on
Case Studies. J. Geochem. Explor. 106699. Contributions to the Science of Rare Earth Element Enrichment in Coal and Coal
Couper, J., Fair, J., Penney, W., Walas, S., 2009. Chemical Process Equipment: Selection Combustion Byproducts. Minerals 1–9.
and Design. Elsevier Science and Technology. Hu, J., Zheng, B., Finkelman, R., Wang, B., Wang, M., Li, S., Wu, D., 2006. Concentration
Dai, S., Finkelman, R., 2018. Coal As A Promising Source of Critical Elements: Progress and Distribution of Sixty-One Elements in Coals from DPR Korea. Fuel 679–688.
and Future Prospects. Int. J. Coal Geol. 155–164. Huang, Q., Noble, A., Herbst, J., & Honaker, R. (2018). Liberation and Release of Rare
Dai, S., Seredin, V., Ward, C., Jiang, J., Hower, J., Song, X., Zhao, C., 2014. Composition Earth Minerals from Middle Kittanning, Fire Clay, and West Kentucky No. 13 Coal
and Modes of Occurrence of Minerals and Elements in Coal Combustion Products Sources. Powder Technology, 242-252.
Derived from High-Ge Coals. Int. J. Coal Geol. 79–97. Huang, Q., Talan, D., Restrepo, J., Baena, O., Kecojevic, V., Noble, A., 2019.
Das, S., Gaustad, G., Sekar, A., Williams, E., 2018. Techno-Economic Analysis of Characterization Study of Rare Earths, Yttrium and Scandium from Various
Supercritical Extraction of Rare Earth Elements from Coal Ash. J. Cleaner Prod. Colombian Coal Samples and Non-Coal Lithologies. Int. J. Coal Geol. 14–26.
Department of Energy. (2017). Report on Rare Earth Elements from Coal and Coal Hughes, K., Singh, R., 1980. The Isolation of Thorium from Monazite by Solvent
Byproducts. Washington DC. Extraction. Hydrometallurgy 25–33.
Doi, K., Hirono, S., Sakamaki, Y., 1975. Uranium Mineralization by Ground Water in Humelnicu, D., Drochioiu, G., Sturza, M., Cecal, A., Popa, K., 2006. Kinetic and
Sedimentary Rocks. Japan. Economic Geology 628–646. Thermodynamic Aspects of U(VI) and Th(IV) Sorption on A Zeolitic Volcanic Tuff.
Dutta, T., Kim, K., Uchimiya, M., Kwon, E., Jeon, B., Deep, A., Yun, S., 2016. Global J. Radioanal. Nucl. Chem. 637–640.
Demand for Rare Earth Resources and Strategies for Green Mining. Environ. Res. Hunter, K.A., Hawked, J., Chool, K., 1988. Equilibrium adsorption ofthorium by metal
182–190. oxides in marine electrolytes. Geo- chim. C’osmochim. Acta 52, 627–636.

17
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Hvistendahl, M., 2007, December 13. Coal Ash Is More Radioactive Than Nuclear Waste. html?pdfurl=https%3A%2F%2Fblue-sea-697d.quartiers047.workers.dev%3A443%2Fhttps%2Fwww.openbriefing.com%2FAsxDownload.aspx%
Retrieved from Scientific American: https://www.scientificamerican.com/article/ 3FpdfUrl%3DReport%252FComNews%252F20140902%252F01549263.
coal-ash-is-more-radioactive-than-nuclear-waste/. pdf&clen=5147313.
IAEA., 2013. Naturally Occurring Radioactive Material (NORM VII): Proceeedings of the Lu, Y., Wei, H., Zhang, Z., Li, Y., Wu, G., Liao, W., 2016. Selective Extraction and
Seventh International Symposium on Naturally Occurring Material. Beijing: IAEA in Separation of Thorium from Rare Earths by a Phosphorodiamidate Extractant.
Austria. Hydrometallurgy 192–197.
Jaffary, N., Khoo, K., Mohamed, N., Yusof, M., Fadzil, S., 2019. Malaysian Monazite and Mackowski, S., Raiter, R., Soldenhoff, K., & Ho, E. (2011). Australia Patent No. U.S.
Its Processing Residue: Chemical Composition and Radioactivity. J. Radioanal. Nucl. 7,993,612 B2.
Chem. https://doi.org/10.1007/s10967-019-06813-1. McLellan, B., Corder, G., Golev, A., Ali, S., 2014. Sustainability of the Rare Earths
Jain, V., Handa, A., Sait, S., Shrivastav, P., Agrawal, Y., 2001. Pre-concentration, Industry. Procedia Environ. Sci. 280–287.
Separation and Trace Determination of Lanthanum(III), Cerium(III), Thorium(IV) Menzies, I., Rigby, F., 1961. Separation of Thorium from Uranium and Rare Earth
and Uranium(VI) on Polymer Supported o-Vanillinsemicarbazone. Anal. Chim. Acta Elements by Solvent Extraction with Tri-n-Butyl Phosphate-Xylene. J. Appl. Chem.
237–246. 104–113.
Jiabao, L., & Jie, L., 2009, 09 07. Rare Earth Industry Adjusts to Slow Market. Retrieved Merdivan, M., Duz, M., Hamamici, C., 2001. Sorption Behaviour of Uranium(VI) with N,
from China Daily: http://www.chinadaily.com.cn/bw/2009-09/07/content_ N-dibutyl-N’-benzoyl thiourea Impregnated in Amberlite XAD-16. Talanta 639–645.
8660849.htm. Metaxas, M., Kasselouri-Rigopoulou, V., Galiatsatou, P., Konstantopoulou, C.,
Jordens, A., 2016. The Beneficiation of Rare Earth Element-Bearing Minerals. McGill Oikonomou, D., 2003. Thorium Removal by Different Adsorbents. J. Hazard. Mater.
University, Montreal. 71–82.
Jorgensen, S. (1989). Chapter 4-Adsorption and Ion Exchange. Developments in Milonjic, S., Cokesa, D., Stevanovic, R., 1992. Dynamic Adsorption of Uranium(VI) and
Environmental Modelling, 65-81. Zirconium(IV) on Silica Gel. J. Radioanal. Nucl. Chem. 79–90.
Jorjani, E., Shahbazi, M., 2016. The Production of Rare Earth Elements Group via Misaelides, P., Godelitsas, A., Filippidis, A., Charistos, D., Anousis, I., 1995. Thorium and
Tributyl Phosphate Extraction and Precipitation Stripping Using Oxalic Acid. Uranium Uptake by Natural Zeolitic Materials. Sci. Total Environ. 237–246.
Arabian J. Chem. 1532–1539. Monhemius, J., 1977. Precipitation Diagrams for Metal Hydroxides, Sulfides, Arsenates
Judge, W., & Azimi, G., 2020. Recent Progress in Impurity Removal During Rare Earth and Phosphates. Trans. Inst. Min. Metall. 202–206.
Element Processing: A Review. Hydrometallurgy, 105435. Monji, A., Ghoulipour, V., Mallah, M., 2016. Selective Sorption of Uranium (IV) from
Jyothi, R., Thenepalli, T., Ahn, J., Parhi, P., Chung, K., Lee, J., 2020. Review of Rare Hydrochloric Acid Media by Agro-Industrial Byproducts. Ann. Nucl. Energy
Earth Elements Recovery from Secondary Resources for Clean Energy Technologies: 115–121.
Grand Opportunities to Create Wealth from Waste. J. Cleaner Prod. 122048. Nakajima, A., Tsuruta, T., 2004. Competitive Biosorption of Thorium and Uranium by
Kammerer, J., Carle, R., Kammerer, D., 2011. Adsorption and Ion Exchange: Basic Micrococcus Luteus. J. Radioanal. Nucl. Chem. 13–18.
Principles and Their Application in Food Processing. J. Agri. Food Chem. Rev. Nandanwar, S., Coldsnow, K., Utgikar, V., Sabharwall, P., Aston, D., 2016. Capture of
22–42. Harmful Radioactive Contaminants from Off-Gas Stream Using Porous Solid
Karayigit, A., Gayer, R., Querol, X., Onacak, T., 2000. Contents of Major and Trace Sorbents for Clean Environment - A Review. Chem. Eng. J. 369–381.
Elements in Feed Coals from Turkish Coal-Fired Power Plants. Int. J. Coal Geol. Nasab, M., 2014. Solvent Extraction Separation of Uranium (VI) and Thorium (IV) with
169–184. Neutral Organophosphorus and Amine Ligands. Fuel 595–600.
Kaynar, U., Ayvacikli, M., Hicsonmez, U., Kaynar, S., 2015. Removal of Thorium(IV) Ions Nasab, M., Sam, A., Milani, S., 2011. Determination of Optimum Process Conditions for
from Aqueous Solutions by A Novel Nanoporous ZnO: Isotherms, Kinetic and the Separation of Thorium and Rare Earth Elements by Solvent Extraction.
Thermodynamic Studies. J. Environ. Radioact. 145–151. Hydrometallurgy 141–147.
Ketris, M., Yudovich, Y., 2009. Estimations of Clarkes for Carbonaceous Biolithes: World Nassar, N., Wilburn, D., & Goonan, T., 2016. Byproduct Metal Requirements for U.S.
Averages for Trace Element Contents in Black Shales and Coals. Int. J. Coal Geol. Wind and Solar Photovoltaic Electricity Generation up to the Year 2040 under
135–148. Various Clean Power Plan Scenarios. Applied Energy, 1209-1226.
Khalili, F., Al-Banna, G., 2015. Adsorption of Uranium(VI) and Thorium(IV) by Navarro, J., & Zhao, F., 2014. Life-Cycle Assessment of the Production of Rare Earth
insolubilized Humic Acid from Ajloun Soil - Jordan. J. Environ. Radioact. 16–26. Elements for Energy Applications: A Review. Retrieved from Frontiers in Energy
Kilislioglu, A., Bilgin, B., 2003. Thermodynamic and Kinetic Investigations of Uranium Research: https://www.frontiersin.org/articles/10.3389/fenrg.2014.00045/full.
Adsorption on Amberlite IR-118H Resin. Appl. Radiat. Isot. 155–160. Navrotsky, A., Shvareva, T., & Guo, X., 2013. Thermodynamics of Uranium Minerals and
Kim, H., Eggert, R., Carlsen, B., Dixon, B., 2016. Potential Uranium Supply from Related Materials. In Mineralogical Association of Canada Short Course 43.
Phosphoric Acid: A U.S Analysis Comparing Solvent Extraction and Ion Exchange Winnipeg, MB.
Recovery. Resour. Policy 222–231. Nekhunguni, P., Tavengwa, N., Tutu, H., 2017. Sorption of Uranium(VI) onto Hydrous
Kim, E., Osseo-Asare, K., 2012. Aqueous Stability of Thorium and Rare Earth Metals in Ferric Oxide-Modified Zeolite: Assessment of the Effect of pH, Contact Time,
Monazite Hydrometallurgy: Eh-pH Diagrams for the Systems Th-, Ce-, La-, Nd- Temperature, Selected Cations and Anions on Sorbent Interactions. J. Environ.
(PO4)-(SO4)-H2O at 25◦ C. Hydrometallurgy 67–78. Manage. 571–582.
Kolker, A., Scott, C., Hower, J., Vazquez, J., Lopano, C., Dai, S., 2017. Distribution of O’Callaghan, J., 2012. Rare Earth Minerals and the Geochemistry and Implications of
Rare Earth Elements in Coal Combustion Fly Ash, Determined by SHRIMP-RG Ion Their Perspective Uranium and Thorium Contents. Cornwall: Camborne School of
Microprobe. Int. J. Coal Geol. 1–10. Mines, University of Exeter.
Korkisch, J., Tera, F., 1961. Separation of Thorium by Anion Exchange. Anal. Chem. Omodara, L., Pitkaaho, S., Turpeinen, E., Saavalainen, P., Oravisjarvi, K., Keiski, R.,
1264–1266. 2019. Recycling and Substitution of Light Rare Earth Elements, Cerium, Lanthanum,
Krebs, D., & Furfaro, D. (2013). The Kvanefjeld Process. ALTA 2013 Uranium-REE Neodymium, and Praseodymium from End-of-Life Applications- A Review. J. Cleaner
Conference. Perth, Australia. Prod. 117573.
Kuang, S., Zhang, Z., Li, Y., Wei, H., Liao, W., 2017. Synergistic Extraction and Ozbayoglu, G., Atalay, M., 2000. Beneficiation of Bastnaesite by A Multi-Gravity
Separation of Rare Earths from Chloride Medium by the Mixture of HEHAPP and Separator. J. Alloy. Compd. 520–523.
D2EHPA. Hydrometallurgy 78–83. Pagano, G., Aliberti, F., Guida, M., Oral, R., Siciliano, A., Trifuoggi, M., Tommasi, F.,
Kumari, A., Panda, R., Jha, M., Kumar, J., Lee, J., 2015. Process Development to Recover 2015. Rare Earth Elements in Human and Animal Health: State of Art and Research
Rare Earth Metals from Monazite Mineral: A Review. Miner. Eng. 102–115. Priorities. Environ. Res. 215–220.
Kursun, I., Tombal, T., Terzi, M., 2018. Solubility of Eskisehir Thorium/Rare Earth Ores Pagano, G., Thomas, P., Di Nunzio, A., Trifuoggi, M., 2019. Human Exposures to Rare
in Sulphuric and Nitric Acids. Physicochem. Probl. Min. Process. 476–483. Earth Elements: Present Knowledge and Research Prospects. Environ. Res. 493–500.
Kutahyali, C., Eral, M., 2010. Sorption Studies of Uranium and Thorium on Activated Page, M., Soldenhoff, K., Ogden, M., 2017. Comparative Study of the Application of
Carbon Prepared from Olive Stones: Kinetic and Thermodynamic Aspects. J. Nucl. Chelating Resins for Rare Earth Recovery. Hydrometallutgy 275–281.
Mater. 251–256. Palmieri, M., 1987. Separation and Determination of Trace Metal Ions Using Organic
Ladeira, A., Goncalves, C., 2007. Influence of Anion Species on Uranium Separation from Chelating Reagents. Iowa State University.
Acid Mine Water Using Strong Base Resins. J. Hazard. Mater. 499–504. Papadopoulos, A., Fatta, D., Parperis, K., Mentzis, A., Haralambous, K., Loizidou, M.,
Lange, C., Camargo, I., Figueiredo, A., Castro, L., Vasconcellos, M., Ticianelli, R., 2017. 2004. Nickel Uptake from A Wastewater Stream Produced in A Metal Finishing
A Brazilian Coal Fly Ash As A Potential Source for Rare Earth Elements. J. Radioanal. Industry by Combination of Ion-Exchange and Precipitation Methods. Sep. Purif.
Nucl. Chem. 1235–1241. Technol. 181–188.
Langmuir, D., 1978. Uranium Solution-Mineral Equilibria at Low Temperatures with Papastefanou, C., 2007. Radioactivity of Coals and Fly Ashes. J. Radioanal. Nucl. Chem.
Applications to Sedimentary Ore Deposits. Geohem. et Cosmochim. Acta 547–569. 29–35.
Lanzerstorfer, C., 2018. Pre-processing of Coal Combustion Fly Ash by Classification for Parzentny, H., Rog, L., 2019. The Role of Mineral Matter in Concentrating Uranium and
Enrichment of Rare Earth Elements. Energy Rep. 660–663. Thorium in Coal and Combustion Residues from Power Plants in Poland. Minerals.
Lin, R., Soong, Y., Granite, E., 2018. Evaluation of Trace Elements in U.S. Coals Using the https://doi.org/10.3390/min9050312.
USGS COALQUAL Database Version 3.0. Part I: Rare Earth Elements and Yttrium Paulick, H., Machacek, E., 2017. The Global Rare Earth Element Exploration Boom: An
(REY). Int. J. Coal Geol. 1–13. Analysis of Resources Outside of China and Discussion of Development Perspectives.
Liu, H., Pan, Z., 2011. NORM Situation in Non-Uranium Mining in China. Ann. ICRP Resour. Policy 134–153.
343–351. Pillai, P., 2017. Naturally Occurring Radioactive Materials (NORM) in the Extraction and
Liu, Y., Wang, Y., Zhang, Z., Cao, X., Nie, W., Li, Q., Hua, R., 2013. Removal of Uranium Processing of Rare Earths. In: Proceedings of An International Symposium.
from Aqueous Solution by A Low Cost and High-Efficient Adsorbent. Appl. Surf. Sci. International Atomic Energy Agency, Seville, Spain, pp. 197–221.
68–74. Pulhani, V., Dafauti, S., Hegde, A., 2012. Separation of Uranium from Iron in
Lockyer, G. (2014, September 2). Retrieved from Nolans Report Underscores Feasibility Groundwater Samples Using Ion Exchange Resins. J. Radioanal. Nucl. Chem.
Study Progress: chromeextension://efaidnbmnnnibpcajpcglclefindmkaj/viewer. 299–302.

18
D. Talan and Q. Huang Minerals Engineering 179 (2022) 107430

Qadeer, R., Hanif, J., Saleem, M., Afzal, M., 1992. Effect of Alkali Metals, Alkaline Earth Udayakumar, S., Baharun, N., Rezan, S., Ismail, A., Takip, K., 2021. Economic Evaluation
Metals and Lanthanides on the Adsorption of Uranium on Activated Charcoal from of Thorium Oxide Production from Monazite Using Alkaline Fusion Method. Nuclear
Aqueous Solutions. J. Radioanal. Nucl. Chem. 243–253. Eng. Technol. https://doi.org/10.1016/j.net.2021.01.028.
Qi, D. (2018). Extractants Used in Solvent Extraction-Separation of Rare Earths: United States Geological Survey. (1997). Retrieved from Radioactive Elements in Coal
Extraction Mechanism, Properties, and Features. In Hydrometallurgy of Rare Earths- and Fly Ash: Abundance, Forms, and Environmental Significance: https://pubs.usgs.
Separation and Extraction (pp. 187-389). gov/fs/1997/fs163-97/FS-163-97.html.
Qin, S., Lu, Q., Li, Y., Wang, J., Zhao, Q., Gao, K., 2018. Relationships Between Trace USGS. (2021, 03 31). Rare Earths Statistics and Information. Retrieved from National
Elements and Organic Matter in Coal. J. Geochem. Explor. 101–110. Minerals Information Center: https://www.usgs.gov/centers/nmic/rare-earths-
Qiu, S., Li, S., Dong, Y., Su, X., Wang, Y., Shen, Y., Sun, X., 2017. A High-Performance statistics-and-information.
Impregnated Resin for Recovering Thorium from Radioactive Rare Earth Waste United States Geological Survey, 1997. Retrieved from Radioactive Elements in Coal and
Residue. J. Mol. Liq. 380–386. Fly Ash: Abundance, Forms, and Environmental Significance: https://pubs.usgs.gov/
Quinn, J., Soldenhoff, K., Stevens, G., Lengkeek, N., 2015. Solvent Extraction of Rare fs/1997/fs163-97/FS-163-97.html. United States Geological Survey.
Earth Elements Using Phosphonic/Phosphinic Acid Mixtures. Hydrometallurgy Vaaramaa, K., Pulli, S., Lehto, J., 2000. Effects of pH and Uranium Concentration on the
298–305. Removal of Uranium from Drinking Water by Ion Exchange. Radiochim. Acta
Rahmati, A., Ghaemi, A., Samadfam, M., 2012. Kinetic and Thermodynamic Studies of 845–849.
Uranium(VI) Adsorption Using Amberlite IRA-910 Resin. Ann. Nucl. Energy 42–48. Valentim, B., Abagiu, A., Anghelescu, L., Flores, D., French, D., Goncalves, P., Ward, C.,
Rand, M., Fuger, J., Grenthe, I., Neck, V., & Rai, D., 2008. Chemical Thermodynamics of 2019. Assessment of Bottom Ash Landfilled at Ceplea Valley (Romania) As A Source
Thorium. Oxford. of Rare Earth Elements. Int. J. Coal Geol. 109–126.
Reynier, N., Gagne-Turcotte, R., Coudert, L., Costis, S., Cameron, R., Blais, j., 2021. Van Gosen, B., Verplanck, P., Seal, R. I., Long, K., & Gambogi, J., 2017. Rare-Earth
Bioleaching of Uranium Tailings as Secondary Sources for Rare Earth Elements Elements, Chap. O ofSchulz, K.J, DeYoung, J.H. Jr, Seal, R.R., II, and Bradley, D.C.,
Production. Minerals 11, 302. eds. Critical Mineral Resources of United States-Economic and Environmental
Rim, K., Koo, K., Park, J., 2013. Toxicological Evaluations of Rare Earths and Their Geology and Prospects for Future Supply: U.S. Geological Survey Professional Paper.
Health Impacts to Workers: A Literature Review. Safety Health at Work 12–26. Van Gosen , B., Vernplanck, P., & Emsbo, P., 2019. Rare Earth Element Mineral Deposits
Rozmaric, M., Ivsic, A., Grahek, Z., 2009. Determination of Uranium and Thorium in in the United States. U.S.Geological Survey Circular 1454.
Complex Samples Using Chromatographic Separation. In: ICP-MS and Vass, C., Noble, A., & Ziemkiewicz, P., 2019. The Occurrence and Concentration of Rare
Spectrophotometric Detection. Talanta, pp. 352–362. Earth Elements in Acid Mine Drainage and Treatment By-products: Part 1-Initial
Salehuddin, A., Ismail, A., Bahri, C., Aziman, E., 2019. Economic Analysis of Thorium Survey of the Northern Appalachian Coal Basin. Mining, Metallurgy and Exploration.
Extraction from Monazite. Nucl. Eng. Technol. 631–640. Vijayalakshmi, R., Mishra, S., Singh, H., Gupta, C., 2001. Processing of Xenotime
Samsonov, M., Trofimov, T., Kulyako, Y., Vinokurov, S., Malikov, D., Batorshin, G., Concentrate by Sulphuric Acid Digestion and Selective Thorium Precipitation for
Myasoedov, B., 2015. Recovery of Rare Earth Elements, Uranium and Thorium from Separation of Rare Earths. Hydrometallurgy 75–80.
Monazite Concentrate by Supercritical Fluid Extraction. Radiochemistry 343–347. Wagner, N., Matiane, A., 2018. Rare Earth Elements in Select Main Karoo Basin (South
Sani, A., Bandegharaei, A., Hosseini, S., Kharghani, K., Zarei, H., Rastegar, A., 2015. Africa) Coal and Coal Ash Samples. Int. J. Coal Geol. 82–92.
Kinetic, Equilibrium and Thermodynamic Studies on Sorption of Uranium and Wang, L., Zhong, B., Liang, T., Xing, B., Zhu, Y., 2016. Atmospheric Thorium Pollution
Thorium from Aqueous Solutions by A Selective Impregnated Resin Containing and Inhalation Exposure in the Largest Rare Earth Mining and Smelting Area in
Carminic Acid. J. Hazard. Mater. 152–163. China. Sci. Total Environ. 1–8.
Sapsford, D., Bowell, R., Geroni, J., Penman, K., Dey, M., 2012. Factors Influencing the Wang, Y., Zhang, Z., Liu, Y., Cao, Z., Liu, Y., Li, Q., 2012. Adsorption of U(VI) from
Release Rate of Uranium, Thorium, Yttrium and Rare Earth Elements from A Low- Aqueous Solution by the Carboxyl-Mesoporous Carbon. Chem. Eng. J. 246–253.
Grade Ore. Miner. Eng. 165–172. Wang, X., Zhu, G., Guo, F., 2013. Removal of Uranium (VI) Ion from Aqueous Solution by
Schreiber, A., Marx, J., Zapp, P., 2021. Life cycle assessment studies of rare earths SBA-15. Ann. Nucl. Energy 151–157.
production - findings from a systematic review. Sci. Total Environ. Wang, D., Zhao, Z., Yu, Y., Dai, J., Deng, M., Zhao, T., Liu, L., 2018. Exploration and
Schreiber, A., Marx, J., Zapp, P., Hake, J., Vobenkaul, D., Friedrich, B., 2016. Research Progress on Ion-Adsorption Type REE Deposit in South China. China Geol.
Environmental Impacts of Rare Earth Mining and Separation Based on Eudialyte: A 415–424.
New European Way. Resources. https://doi.org/10.3390/resources5040032. Wang, L., Huang, X., Yu, Y., Zhao, L., Wang, C., Feng, Z., Long, Z., 2017. Towards Cleaner
Schuler, D., Buchert, M., Liu, R., Dittrich , S., & Merz, C. (2011). Study on Rare Earths Production of Rare Earth Elements from Bastnaesite in China. J. Cleaner Prod.
and Their Recycling. Darmstadt. 231–242.
Semnani, F., Asadi, Z., Samadfam, M., Sepehrian, H., 2012. Uranium(VI) Sorption Xiong, X., Tao, Y., Yu, Z., Yang, L., Sun, L., Fan, Y., Luo, F., 2020. Selective Extraction of
Behavior onto Amberlite CG-400 Anion Exchange Resin: Effects of pH, Contact Time, Thorium from Uranium and Rare Earth Elements Using Sulfonated Covalent Organic
Temperature, and Presence of Phosphate. Ann. Nucl. Energy 21–24. Framework and Its Membrane Derivative. Chem. Eng. J. 123240.
Shimidt, V., 1971. Amine Extraction. Keter Press, Jerusalem. Xu, Z., Huang, X., Wan, L., 2009. Surface Engineering of Polymer Membranes. Springer,
Sikalidis, C., Alexiades, C., Misaelides, P., 2008. Adsorption of Uranium and Thorium Hangzhou.
from Aqueous Solutions by the Clay Minerals Montmorillonite and Vermiculite. Yadav, V., Gadi, R., Kalra, S., 2019. Clay Based Nanocomposites for Removal of Heavy
Toxicol. Environ. Chem. 175–180. Metals from Water: A Review. J. Environ. Manage. 803–817.
Silva, R.G., De Morais, C.A., Teixeria, L.V., 2018. Selective Removal of Impurities from Yang, X., 2019. Leaching Characteristics of Rare Earth Elements from Bituminous Coal-
Rare Earth Sulphuric Liquor Using Different Reagents. Miner. Eng. 238–246. Based Sources. University of Kentucky, Lexington.
Silva, R., Morais, C., Oliveira, E., 2019. Selective Precipitation of Rare Earth from Non- Yakout, S., 2017. Influence of Solution Chemistry on the Selective Adsorption of
purified and Purified Sulfate Liquors Using Sodium Sulfate and Disodium Hydrogen Uranium and Thorium onto Activated Carbon. Nucl. Technol. 294–300.
Phosphate. Miner. Eng. 402–416. Yang, J., Montross, S., Britton, J., Stuckman, M., Lopano, C., Verba, C., 2020.
Song, Y., Wang, Y., Wang, L., Song, C., Yang, Z., Zhao, A., 1999. Recovery of Uranium Microanalytical Approached to Characterizing REE in Appalachian Basin
from Carbonate Solutions Using Strongly Basic Anion Exchanger 4. In: Column Underclays. Minerals. https://doi.org/10.3390/min10060546.
Operation and Quantitative Analysis. Reactive and Functional Polymers, Youssef, W., Hagag, M., Ali, A., 2018. Synthesis, Characterization and Application of
pp. 245–252. Composite Derived from Rice Husk Ash with Aluminum Oxide for Sorption of
Stegen, K., 2015. Heavy Rare Earths, Permanent Magnets, and Renewable Energies: An Uranium. Adsorpt. Sci. Technol. 1274–1293.
Imminent Crisis. Energy Policy 1–8. Zhang, P., Liang, H., Jin, Z., DePaoli, D., 2017. The ultimate mineral processing
Su, J., Xu, R., Ni, S., Li, F., Sun, X., 2020. A Cost-Effective Process for Recovering challenge: Recovery of rare earths, phosphorus and uranium from Florida phosphatic
Thorium and Rare Earths from Radioactive Residues. J. Cleaner Prod. 119932. clay. Miner. Metall. Process. 34 (4), 183–188.
Suli, L., Ibrahim, W., Aziz, B., Deraman, M., Ismail, N., 2017. A Review of Rare Earth Zhang, W., Honaker, R., 2018. Rare Earth Elements Recovery Using Staged Precipitation
Mineral Processing Technology. Chem. Eng. Res. Bullet. 20–35. from A Leachate Generated from Coarse Coal Refuse. Int. J. Coal Geol. 189–199.
Talan, D., Huang, Q., 2020. Separation of Thorium, Uranium and Rare Earths from A Zhang, W., Honaker, R., 2019. Calcination Pretreatment on Acid Leaching Characteristics
Strip Solution Generated from Coarse Coal Refuse. Hydrometallurgy 105446. of Rare Earth Elements from Middlings and Coarse Refuse Material Associated with
Talan, D., Huang, Q., 2021. Separation of Radionuclides from A Rare Earth-Containing A Bituminous Coal Source. Fuel 130–145.
Solution by Zeolite Adsorption. Minerals 11, 1. Zhang, J., Zhao, B., 2016. Separation Hydrometallurgy of Rare Earth Elements. Springer,
Torapava, N., Persson, I., Eriksson, L., Lundberg, D., 2009. Hydration and Hydrolysis of Saskatoon.
Thorium (IV) in Aqueous Solution and the Structures of Two Crystalline Thorium(IV) Zhou, H., Wang, Y., Guo, X., Dong, Y., Su, X., Sun, X., 2018. The Recovery of Rare Earth
Hydrates. Inorg. Chem. 11712–11723. by A Novel Extraction and Precipitation Strategy using Functional Ionic Liquids.
Tsezos, M., Volesky, B., 1982. The Mechanism of Thorium Biosorption by Rhizopus J. Mol. Liq. 414–420.
Arrhizus. Biotechnol. Bioeng. 955–969. Zhu, Z., Han, Y., Luo, X., Long, Z., & Huang, X. (2006). Enrichment and Recovery of
U.S. Environmental Protection Agency. (1999). Understanding Variation in Partition Thorium from Baotou Rare Earth Concentrate. Proceedings of 5th Academic
Coefficient, Kd, Values, Volume II: Review of Geochemistry and Available Kd Values Conference for Chinese Rare Metals. Hunan Changsha.
for Cadmium, Cesium, Chromium, Lead, Plutonium, Radon, Strontium, Thorium, Zhu, Z., Pranolo, Y., Cheng, C., 2015. Separation of Uranium and Thorium from Rare
Tritium, and Uranium. Washington, DC: U.S. Environmental Protection Agency and Earths for Rare Earth Production: A Review. Miner. Eng. 185–196.
U.S. Department of Energy. Zou, W., Zhao, L., Han, R., 2009. Removal of Uranium (VI) by Fixed Bed Ion-Exchange
Uda, T., Jacob, K., Hirasawa, M., 2000. Technique for Enhanced Rare Earth Separation. Column Using Natural Zeolite Coated with Manganese Oxide. Chin. J. Chem. Eng.
Science 2326–2329. 585–593.

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