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Dutta 2016

This article discusses the growing global demand for rare earth elements, which are essential materials for renewable energy and electronic technologies. Demand is expected to increase by 5% annually through 2020. Currently, China supplies 85% of the world's rare earth oxide production. To ensure a stable supply, new strategies are needed to develop domestic rare earth resources and improve recycling. There is also a need for more efficient use of rare earths in devices and to recover them from waste streams. Addressing the environmental, economic, and social challenges of rare earth mining will be important to develop a sustainable supply of these critical materials.

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0% found this document useful (0 votes)
26 views

Dutta 2016

This article discusses the growing global demand for rare earth elements, which are essential materials for renewable energy and electronic technologies. Demand is expected to increase by 5% annually through 2020. Currently, China supplies 85% of the world's rare earth oxide production. To ensure a stable supply, new strategies are needed to develop domestic rare earth resources and improve recycling. There is also a need for more efficient use of rare earths in devices and to recover them from waste streams. Addressing the environmental, economic, and social challenges of rare earth mining will be important to develop a sustainable supply of these critical materials.

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Environmental Research 150 (2016) 182–190

Contents lists available at ScienceDirect

Environmental Research
journal homepage: www.elsevier.com/locate/envres

Review article

Global demand for rare earth resources and strategies for green mining
Tanushree Dutta a, Ki-Hyun Kim a,n, Minori Uchimiya b, Eilhann E. Kwon c,
Byong-Hun Jeon d, Akash Deep e, Seong-Taek Yun f
a
Department of Civil & Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea
b
USDA-ARS Southern Regional Research Center, 1100 Robert E. Lee Boulevard, New Orleans, LA 70124, United States
c
Department of Environment and Energy, Sejong University, Seoul 05006, Republic of Korea
d
Department of Natural Resources & Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea
e
Central Scientific Instruments Organisation (CSIR-CSIO), Sector 30C, Chandigarh 160030, India
f
Department of Earth and Environmental Sciences and KU-KIST Green School, Korea University, Seoul 02841, Republic of Korea

art ic l e i nf o a b s t r a c t

Article history: Rare earth elements (REEs) are essential raw materials for emerging renewable energy resources and
Received 22 March 2016 ‘smart’ electronic devices. Global REE demand is slated to grow at an annual rate of 5% by 2020. This high
Received in revised form growth rate will require a steady supply base of REEs in the long run. At present, China is responsible for
28 May 2016
85% of global rare earth oxide (REO) production. To overcome this monopolistic supply situation, new
Accepted 30 May 2016
strategies and investments are necessary to satisfy domestic supply demands. Concurrently, environ-
mental, economic, and social problems arising from REE mining must be addressed. There is an urgent
Keywords: need to develop efficient REE recycling techniques from end-of-life products, technologies to minimize
Rare earth ore deposits the amount of REEs required per unit device, and methods to recover them from fly ash or fossil fuel-
Ion-adsorption
burning wastes.
Urban mining
& 2016 Elsevier Inc. All rights reserved.
Preservation
Recycling

1. Introduction 2020. Therefore, it has become obligatory for REE-consuming na-


tions to create align supply chains for REEs in order to maintain
A gradual shift from traditional energy sources towards green current technologies and develop advanced technologies involving
energy alternatives such as solar cells, electric vehicles, and wind renewable energy resources.
turbines is becoming realized on a global scale. The transition has Rare earths are actually not rare to exhibit a broad geographical
led to a rapid surge in demand for a critical commodity: rare earth distribution. The average levels of REEs in the earth's crust range
elements (REEs). REEs are crucial for manufacturing a broad array from 150 to 220 ppm (ppm) which exceed the level of many other
of high-tech products, devices, and technologies with widespread metals mined for industrial use (e.g. copper: 55 ppm and zinc: 70
applications in the medical, defense, aerospace, and automobile ppm) (Long et al., 2010). Nonetheless, establishing and maintain-
industries (Figs. 1,2). International Union for Pure and Applied ing a reliable supply chain of REEs are of great concern for a
Chemistry (IUPAC) defines REEs as the group of 17 elements number of reasons. Rare earths occur in geological deposits in
comprising 15 lanthanides plus Yttrium and Scandium (Table 1). combination with other materials, which makes the extraction of
Rare earth elements are subdivided into heavy rare earth elements pure REEs challenging and expensive. The supply of standard
(HREE) and light rare earth elements (LREE). Lanthanum, cerium, grade REEs depends upon the geology of the ores, cost of extrac-
tion, market demand, and price of individual REEs. A key concern
praseodymium, neodymium, promethium, and samarium are
is whether the current supply base of REEs can keep pace with the
LREEs, while yttrium, europium, gadolinium, terbium, dysprosium,
projected growth of REE markets worldwide. For example, there
holmium, erbium, thulium, ytterbium, and lutetium constitute
was volatility in the rhenium market due to its under-supply in
HREEs. The global market of REE-based products is estimated to be
2008, which caused an excessive price hike (10,500 USD/kg)
worth 1.5–2 trillion US dollars, based on trade information and REE
(Global Information Market Research Report, 2015). If these types
contents of manufactured goods (Tukker, 2014). According to the
of situations arise for REEs, the resilience of the supply chain will
United States Geological Survey (USGS), 2016 report, the annual
be decided by the supply chain's resistance, speed of response, and
growth rate of global REE demand is expected to increase by 5% by flexibility to market fluctuations (refer to the case study of neo-
dymium by Sprecher et al. (2015). In addition, in order to ensure
n
Corresponding author. zero surplus of any REEs, a maintenance of the right balance be-
E-mail address: [email protected] (K.-H. Kim). tween the supply and demand is of paramount significance for

http://dx.doi.org/10.1016/j.envres.2016.05.052
0013-9351/& 2016 Elsevier Inc. All rights reserved.
T. Dutta et al. / Environmental Research 150 (2016) 182–190 183

Fig. 1. Major areas of consumption of REEs worldwide. Percentage values indicate forecasted industry-level annual growth rate (Alonso et al., 2012) of each REE demand
category using the projections used for 2015–2035 (Kingsworth, 2010), assuming that each REE consumption market will grow at rates predicted by industry experts.

economic reasons (Binnemans and Jones, 2015). The deviation of


balance can be caused by the reduced availability of the more
important REEs and vice versa. Recycling of the critical REEs could
be an appropriate solution for this problem.
Above-outlined concerns have motivated both developing and
developed nations to secure REE reserves. Most countries relied
heavily on imports for their current REE demands; in some cases,
100% of REEs were reported to be imported. However, this trend
has been changing rapidly most likely due to the restrictions re-
cently imposed by China on the export of metals and mineral
products (Mancheri et al., 2015). The USGS commodity report for
the fiscal year of 2015–2016 revealed that the United States de-
creased its import of rare earth metals and compounds from $190
million in 2014 to $150 million (estimated) in 2015. Up till 2010,
China controlled 98% of the global REE production (Chakhmour-
Fig. 2. REE usage (%) by types of application fields (adopted from Binnemans and
Jones, 2014). adian and Wall, 2012). Such market monopolies are detrimental
because even small changes in the foreign policy and export

Table 1
Summary of the usage of different REEs.

Serial No. REE Symbol Atomic number Use

1. Scandium Sc 21 Aerospace framework, high-intensity street lamps, high-performance equipment such as bicycle frames,
baseball bats
2. Yttrium Y 39 Television and computer screens, LED lights, cancer treatment drugs, enhances strength of alloys, catalyst
3. Lanthanum La 57 Camera lenses, carbon lighting applications such as studio lighting and projector lights, battery electrodes
4. Cerium Ce 58 Catalytic converters in cars, colored glass, steel production, refining crude oils
5. Praseodymium Pr 59 Strong magnets, welding goggles, lasers, aircraft engines
6. Neodymium Nd 60 Powerful magnets used in computed HD, microphones, wind turbines, and hybrid cars, lasers
7. Promethium Pm 61 Not usually found in nature
8. Samarium Sm 62 Cancer treatment, nuclear reactor control rods, X-ray lasers
9. Europium Eu 63 Color television screens, computer screens, fluorescent glass, genetic screening tests, control rods in nuclear
reactors
10. Gadolinium Gd 64 X-ray & MRI scanning systems, shielding in nuclear reactors, increases durability of alloys, green phosphors in
television screens
11. Terbium Tb 65 Television and computer screens, fuel cells, solar systems
12. Dysprosium Dy 66 Commercial lighting, hard disk devices, transducers
13. Holmium Ho 67 Lasers, glass coloring, high-strength magnets
14. Erbium Er 68 Glass colorant, signal amplification in fiber optic cables, metallurgical uses
15. Thulium Tm 69 High-efficiency lasers, portable X-ray machines, high temperature superconductors
16. Ytterbium Yb 70 Improves stainless steel, lasers, ground monitoring devices, industrial catalysts
17. Lutetium Lu 71 Cracking hydrocarbons in oil refineries
184 T. Dutta et al. / Environmental Research 150 (2016) 182–190

Fig. 3. Historical trend of the mine production of REO (in tons) in the world and China (according to USGS). The shaded area indicates the decreasing share of China in the
world production of REEs from more than 95% before 2012 down to 85% in 2015.

criteria of one country can lead to inimical instabilities of global prevent steady declination of one of the earth's critical resources
market. The control of China over the world mine production of are also suggested.
rare earth oxides has indeed gone down significantly in the last
three years. Fig. 3 shows the decreasing share of China (85%
shareholder) in the world mine production of rare earths. Never- 2. Rare-earth resources
theless, in various places, the mining of REEs in socially and en-
vironmentally unacceptable ways has placed this industry under Rare earth elements occur in a number of mineral deposits;
global scrutiny, further accentuating supply risk. The example of however, they are not concentrated enough (typical concentration
Kvanefjeld, recognized as one of the world's largest REE resources, range is 10 to a few hundred ppm by weight) to make their mining
illustrates the fact that even highly environmentally conscious and easy or economic (Long et al., 2010). The most abundant mineral
progressive countries like Greenland (an autonomous Danish ter- sources of REEs, particularly light REEs (LREE), are bastnäsite
ritory) are loosening regulations to allow mining of REEs. [(Ce,La)CO3(F,OH)] and monazite [(Ce,La,Nd,Th)PO4]. Bastnäsite
British Geological Survey Risk List (2015) described REEs as deposits in China and the United States constitute the largest
critically at-risk marketable elements. Particularly, the five ele- percentage of the world’s rare-earth resources, while monazite
ments of dysprosium, terbium, yttrium, europium, and neody- deposits in Australia, Brazil, China, India, Malaysia, South Africa, Sri
mium are critical commodities for emerging clean energy tech- Lanka, Thailand, and the United States constitute the second lar-
nologies. This is primarily due to the fact that the replacement of gest segment (Long et al., 2010). Sources of HREEs include apatite,
such crucial components commonly used in emerging green en- cheralite, eudialyte, loparite, phosphorites, rare-earth-bearing (ion
ergy technologies and smart devices with other more abundant adsorption) clays, secondary monazite, spent uranium solutions,
metals would require compromise for the quality of the finished and xenotime (Long et al., 2010). Rare earth-bearing mineral de-
products. This review aims to provide an updated understanding posits are mainly associated with igneous rocks (alkaline rocks and
of the complex global scenario and risks (in social, environmental, carbonatites) (Long et al., 2010). Furthermore, placer deposits,
and economic) associated with the growth of the REE market and residual deposits from deep weathering of igneous rocks, peg-
possible ways to tackle these risks. Our ultimate goal is to assess matites, iron oxide copper-gold deposits, and sedimentary marine
the future of REE supply chains (Fig. 4), highlight vulnerabilities phosphate deposits (phosphorites) also contain economically vi-
for REE-consumers, and propose ways to combat the environ- able REE concentrations (Table 2). Recent studies of Aiglsperger
mental impacts of REE mining. Alternatives and measures to et al. (2016) suggest nickel laterites of Cuba (Mao Bay area) and
Dominican Republic (Falcondo mines) as a worthy target of critical
metals like REEs.
In addition to the occurrences in the form of ores and deposits,
rare earths are also found in coal and coal by-products (in sedi-
mentary rocks) at a very low concentration. As such, their recovery
from such sources is economically implausible. Several sources of
information concerning the REE contents in coal samples from
different countries are available (See Seredin et al., 2013 and
Blissett et al., 2014). For example, Seredin et al. (2013) reported
0.002–0.8% of Ge, Ga, Se, and Li in coal deposits, wherein rare
metal contents were only reported from laboratorial ashes in high-
temperature, e.g., between 600 and 850 °C (that excludes the vo-
latile fractions of the metals). Despite the low concentrations of
REEs in coal by-products, they have been suggested to be im-
portant for their recovery; their presence can ultimately help ex-
Fig. 4. Anticipated evolution of global rare earth demand and supply from 2016 to pand REE reserve and production (Rozelle et al., 2016). Moreover,
2020. Data for this plot were extracted from Rollat et al. (2016). fly ashes arising due to coal combustion and from municipal solid
T. Dutta et al. / Environmental Research 150 (2016) 182–190 185

Table 2 waste incinerators (MSWI) have been found to comprise a sig-


Classification of rare earth-bearing mineral deposits. (Source: Long et al., 2010). nificant fraction of REEs. Hard coal fly ashes, for instance, re-
portedly contain 445 mg kg  1 REEs on an average global basis
Serial No. Rocks and deposits Type
(Ketris and Yudovich, 2009). On the other hand, the total con-
1. Peralkaline igneous rocks Magmatic (alkali-ultrabasic) centration of REEs in the treated bottom ashes from MSWI was
Pegmatite dikes (alkali-ultrabasic) estimated at 110 mg kg  1, with the preferential dominance of La,
Pegmatite dikes (peralkaline)
Ce, and Nd at concentrations greater than 20 mg kg  1 (Allegrini
Hydrothermal veins and stockworks
Volcanic
et al., 2014). Generally, these values are however two to three
Metasomatic-albitite orders of magnitude lower than the typical levels in REE-con-
centrated ores (mentioned before).
2. Carbonatites Magmatic
Dikes and dialational veins
Hydrothermal veins and stockworks
Skarn 3. Mining rare earths
Carbonate rock replacement
Metasomatic-fenite
Rare earth resources are diverse in their geology, mineralogy,
3. Iron oxide-Copper Gold Magnetite-apatite replacement
and REE contents. A series of specific techniques are required to
Hematite-magnetite breccia
process diverse REE resources to extract commercially viable
4. Pegmatites Abyssal (heavy rare earth elements) elements.
Abyssal (light rare earth elements)
Muscovite (rare earth elements)
Rare earth elements-allanite-monazite 3.1. Methods of extraction from major REE resources
Rare earth elements-euxenite
Rare earth elements-gadolinite 3.1.1. Commercial REE ore concentration
Miarolitic-rare earth elements-topaz-
Rare earth ore mining and concentration are performed using a
beryl
Miarolitic-rare earth elements-gadoli- complex (and often economically unrealistic) method that in-
nite-fergusonite cludes REE mining from ore deposits, grinding, cracking the mi-
5. Porphyry molybdenum Climax-type
nerals to produce mixed rare earth oxides (REO) concentrates,
6. Metamorphic Migmatized gneiss separation, purification of oxides, and refining to produce in-
Uranium-rare earth elements skarn dustrial grade REEs (Fig. 5). It is difficult to obtain REE concentrates
7. Stratiform phosphate Platform phosphorite from ore deposits (e.g. bastnäsite and monazite) because they
residual occur in solid-state mineral phase and are often laced with
Carbonatite-associated radioactive elements such as uranium and thorium. Further details
Granite-associated laterite
of the REO present in rare earth minerals and the physical/che-
Baddeleyite bauxite
Karst bauxite mical steps of their processing to obtain ore concentrates (mining,
physical beneficiation like floatation, gravity separation, electro-
8. Paleoplacer Uraniferous pyritic quartz pebble
conglomerate
static, and magnetic separation), processing of concentrates by
Auriferous pyritic quartz pebble leaching in acidic or alkaline medium, pre-concentration, and re-
conglomerate covery of REEs from each solution through precipitation and sol-
9. Placer Shoreline Ti-heavy mineral placer vent extraction methods, can be obtained in recent reviews of
Tin stream placer Kumari et al. (2015) (Monazite) and Sinha et al. (2016) (Bastnasite
and Monazite). The system and process of selective REE extraction

Fig. 5. Steps of REE ore concentration procedure and recycling.


186 T. Dutta et al. / Environmental Research 150 (2016) 182–190

from Bastnasite and Monazite has been patented by Teixeira et al. phosphorites is high enough to be considered, as a primary source
(2015). In addition, many contemporary reports, like Quinn et al. of REEs. For example, some U.S. phosphorites are considerably
(2015) (solvent extraction), based exclusively on REE extraction enriched in REEs (relative to Chinese clay-type of deposits) with
efficiencies by various precipitation and solvent extraction meth- total REE contents in 500–2000 mg Kg  1 (Kato et al., 2011). Most
ods are also available. importantly, unlike primary ore concentrates, phosphorites are
Various techniques are available for the determination of easily extractable. It is noteworthy that the world's fertilizer in-
commercial REE ore concentration. Among those options, one can dustry used phosphorites to produce 150 metric ton phosphate
rely on inductively coupled plasma-optical emission spectroscopy fertilizer per year (Zhang et al., 2006). Phosphate rock is dissolved
(ICP-OES), neutron activation analysis (NAA), and inductively in dilute sulfuric acid to produce phosphoric acid used for the
coupled plasma-mass spectroscopy (ICP-MS) to produce the best production of fertilizer, animal feed, and chemicals. The same
results due to high sensitivity (can detect up to a few ng (10  9 g) process can be used to dissolve 100% of REEs contained in the
L  1 levels) for multi-elements (Zawisza et al., 2016; Li et al., 2016). phosphate deposits (Emsbo et al., 2015). An additional benefit of
Recently, in situ measurement techniques involving the use of phosphate mining is that it does to lead to radioactive thorium or
small, portable equipment for the detection of REEs have also uranium-rich waste commonly associated with REE mining (Zie-
been developed. For instance, portable X-ray fluorescence (pXRF) linski et al., 1997). Collectively, all these factors can make phos-
analyzers were used by Simandl et al. (2014) as field tools to phorites a very useful future resource. Another phosphate ore
detect REEs in sedimentary phosphate deposits. The pXRF data deposit used in the preparation of phosphorus fertilizer, named
were correlated with inductively coupled plasma-atomic emission apatite (containing 0.1–1 mg Kg  1 REO), was tested recently for
spectroscopy (ICP-AES) and ICP-MS data. In addition, magnetic REE recovery (Ogata et al., 2016) in which up to 70% leaching ef-
susceptibility analyzers have also emerged as reliable alternative ficiency of REE was achieved with 2(M) sulfuric acid.
tools for field measurement of REEs (Funari et al., 2016). Although
these portable tools may be less accurate than laboratory mea- 3.1.4. Coal and coal by-products
sures, the above-discussed portable tools are useful enough to Rozelle et al. (2016) reported a recovery rate of 71–89% based
detect the presence of REEs in waste heaps. Moreover, bio-ad- on extraction of REEs from high ash-containing by-products of coal
sorption of REEs from primary ores with the aid of genetically mining collected from a surface coal-mine of the Allegheny group
engineered microbial probes is also a promising technique to as- in Central Pennsylvania. REE concentration profiles above and
sess REE enrichment and/or separation. Park et al. (2016) have below the coal bed were also assessed. The chemical steps for the
recently made a remarkable breakthrough in this emerging re- recovery of REEs involved the use of ammonium sulfate, which
search area by engineering the aerobic bacterium Caulobacter leached out 89% of the REEs into the filtered solution. Subsequent
crescentus that exhibited high specificity toward REEs with small applications of an ionic liquid (1-butyl 3-methylimidazolium
atomic radii through the cell surface display of lanthanide binding chloride) and a deep eutectic solvent (2:1 urea/choline chloride,
tags (LBT). M/M) as lixiviants resulted in 80% and 71% recovery of REEs, re-
spectively. Quantitative analysis of the different REEs was per-
3.1.2. Ion-adsorption clays formed using ICP-AES, which allowed detection of the various
The recovery of REEs from ion-adsorption clays involves rela- REEs (with the exceptions of Dy, Eu, Ho, Lu, Tb, and Tm) with a
tively easy processing steps. These resources are commonly found detection limit (DL) of 5 mg kg  1. In another study, Phuoc et al.
in Madagascar, Brazil and the southern provinces of China (Rocha (2016) used laser-induced breakdown spectroscopy (LIBS) for
et al., 2013; Yang et al., 2013; SGS, 2014). Chemical weathering and qualitative detection of REEs in ash samples of Powder River Basin
dissolution of granite and granite porphyry, where REEs become bituminous coal. Labutin and Popov (2016), however, pointed out
absorbed on the clay surface, result in the formation of ion-ad- the presence of Fe may have led to overlapping spectral lines, thus
sorption clays. Unlike ores, ion-adsorption clays contain REEs in an bringing into question the validity of the spectroscopic data pre-
easily extractable trivalent cationic state. Extraction of rare earths sented by Phuoc et al. (2016).
from these clays is accomplished by surface/mountain-top mining,
followed by tank or heap leaching with aqueous electrolyte solu- 3.1.5. Fly ash from fossil fuel and other wastes
tion (sodium chloride (NaCl)) or ammonium sulfate ((NH4)2SO4), As stated earlier in Section 2, fly ash from MSWI and coal
and finally use of ion-exchangers. The ion exchange reaction be- combustion comprise of extractable amounts of REE (Hower et al.,
tween kaolinite (a hydrated aluminosilicate crystal with chemical 2015; Yuzhuang et al., 2015; Funari et al., 2016). However, those
formula: Al2Si2O5(OH)4 and (NH4)2SO4) can be chemically re- materials are not routinely analyzed due to their low REE content
presented as and apprehensions about the economic viability of the extraction
process. Chemical analyses (using Na2O2 sintering technique cou-
2(Kaolin)3- RE3 þ þ 3(NH4)2SO4-2(Kaolin)3-(NH4 þ )3
pled with ICP-MS) of samples of MSWI fly ashes from incineration
þ(RE3 þ )2(SO42  )3
plants have indicated that they are promising alternative waste-
The above type of ion exchange processing is of industrial derived sources of REEs. Study of fly ash from Jungar power plant,
significance despite limited use of ion-adsorption clays as a rare Inner Mongolia, China by Dai et al. (2014), revealed that the con-
earth reserve. Ion-adsorption rare earths constitute only 2.9% of centration of the critical REEs were greater in the finer sized
China's REE reserves, yet accounting for 26% of China's total REE fractions (454 LREE mg g  1 in o25 mm fraction) of fly ash than the
production during 1988–2007. The figure increased to 35% after coarser ones (156 mg g  1 in 4125 mm fraction). However, the
2009 (Su, 2009; Yang et al., 2013). Nonetheless, a strong reliance feasibility of recovering REEs from fly ash on an industrial scale
upon such small reserve could be detrimental, especially from needs to be explored.
China's point of view as it could result in the fast depletion of their
important natural resources. 3.2. Consequences of rare earth mining

3.1.3. Sedimentary phosphate deposits (phosphorites) Rare earth mining and extraction procedures constitute mas-
REEs are also found to be significantly enriched sedimentary sive exploitation of earth's resources and destabilize/deteriorate
marine phosphate deposits or phosphorites. According to Emsbo soil and water ecosystems. One of the biggest concerns of REE
et al. (2015), the concentration of REEs, particularly of HREEs, in mining from the primary ore deposits such as bastnasite and
T. Dutta et al. / Environmental Research 150 (2016) 182–190 187

monazite is the resultant radioactive stockpiles. Rare earths fre- 2015). On the other hand, development of new technologies to
quently co-exist with radioactive minerals like thorium and ur- make use of lower amounts of the materials is also of great sig-
anium imparting radiological effects during their recovery (Bin- nificance, particularly for some critical REEs, e.g., dysprosium (Dy)
nemans et al., 2013; Ault et al., 2015). The release of the radio- and neodymium (Nd). Such rare earth metals are in high demand,
nucleotides along with other contaminants like dust and heavy as they are used in clean energy technologies (e.g., wind turbines
metals may also bear serious environmental costs. Processing one and electric vehicles) (Fig. 2) (Alonso et al., 2012).
ton of REEs is associated with the generation of 2000 t of toxic
waste and 1000 t of wastewater contaminated with ammonium 4.1. Re-use of REEs through urban mining
sulfate and heavy metals (Su, 2009). Immediate negative effects of
REE mining include severe soil erosion, biodiversity loss, land use Recovery of REEs from scraps formed during production pro-
change, flooding, pollution of air, soil, and water, and crop uptake cesses, landfills, and end-of-life consumer products (e.g., used
of REEs, consequentially leading to human health issues (Tang and cars) is referred as ‘urban mining’ and rightly regarded as an im-
Li, 2000; Liu, 2002; Chen, 2010; Anonymous, 2011; Carpenter portant component of resource management (Simoni et al., 2015;
et al., 2015). Using satellite imagery, Guo (2012) depicted the vi- Bandara et al., 2016). A recent work of Zeng et al. (2016) has also
sual changes in the landscape caused by the surface/mountaintop uncovered newly the potential of waste electronic and electrical
mining in the Ganzhou area of the Jianxi province of China. Bio- equipment (WEEE) or e-waste. The recycling of REEs is also
logical, environmental, and human health effects of mountaintop deemed necessary to counter the harmful effects of extensive
mining activities have been well documented (Gilbert, 2010; mining on the environment (Simoni et al., 2015). In fact, REEs
Holzman, 2011; Beggs, 2012; Bernhardt et al., 2012). Alarmingly, contained in non-recycled waste materials may end up in surface
some of these human health and environmental impacts are ir- waters and oceans. Recently, significantly high concentrations of
reversible and persistent even after reclamation of the mine site rare earths were detected in the surface water of San Francisco Bay
(Palmer et al., 2010). area presumably due to the wastewater treatment plant dis-
China adopted an alternative technique in 1997, which is re- charges of refractory magnetic resonance imaging (MRI) contrast
ferred to as in-situ leaching of clays. This technique deploys agents used in hospitals and medical research centers (Hatje et al.,
leaching holes 0.8 m in diameter and 1.5–3 m in depth at an in- 2014, 2016). Urban mining might be a useful solution to tackle
termittent distance of 2–3 m. Leaching occurs over a prolonged some of these undesired effects of REE mining and discharge
period of time (150–400 days) with application of 3–5% ammo- (Ongondo et al., 2016; Sun et al., 2016). Besides, unlike the primary
nium sulfate solution (Yang et al., 2013). This in-situ leaching REE ores, REE recyclates do not contain radioactive substances,
protects the soil and vegetation. Nevertheless, enforcement of implying that health problems can be partially avoided by means
such in-situ leaching must be preceded by a thorough geotechnical of recycling (Binnemans et al., 2013).
survey of the mining area and nearby locations. Otherwise, there A major challenge in REE recycling has been their low yield rate
may be low REE recovery (up to 5%), groundwater contamination, due to the lack of appropriate recycle design along with the te-
an increase in soil and water pH, and nutrient pollution of dious steps involved in their separation. Likewise, there is a
downstream rivers (Liu, 2002; Palmer et al., 2010). common belief that it is virtually impossible to recycle REEs in any
appreciable quantity, as they are used in very minute quantities. In
this review, a contradictory viewpoint on this generic belief is
4. Preservation of rare earths and sustainability of material discussed by presenting contemporary examples regarding re-
supply chain covery of rare earth metals and oxides from a range of end-of-life
(EoL) products (including spent fluorescent lamps, motors, NiMH
Preservation of rare earth resources calls for the development batteries, fluid catalysts, fuel cell catalysts, etc).
of efficient recycling techniques at the pilot-plant scale. Due to the Table 3 lists 2016 studies on REE recovery from spent products.
economic and environmental costs of REE mining, it is desirable to Similar studies conducted up to 2015 were reviewed by Binne-
promote the recycling and reuse of rare earths, while also mini- mans et al. (2013, 2015) and Tunsu et al. (2015). Most importantly,
mizing the dependency on such resources. Recycling of REEs may many of these studies confirm a reasonably good yields (i.e., up to
help reduce the imbalance in REE supply by enforcing the primary 99%) of re-usable REEs and their oxides, which further exemplifies
supply chain for some REEs that are crucial in particular for in- that recent technological advancements have been able to par-
dustrial applications (Binnemans and Jones, 2015; Machacek et al., tially, if not fully, cross the barriers of REE recycling processes. As a

Table 3
List of 2016 studies on recycling of REEs from end-of-life products.

Order Recycle REE Method used % Recovery Reference

1 Motors Nd, Pr, Dy Hydrometallurgy 82 (99% purity) Bandara et al., 2016


2 Permanent Magnet Nd, Pr Vacuum Induction melting, hydrolysis & magnetic 93 (99.7% purity) Bian et al., 2016
separation
3 Fuel cell catalyst Pt Hydrometallurgy 76 Duclos et al. 2016
4 Phosphor (lamps) Eu, Y Hydrometallurgy 100 (99.9% purity) Dupont and Binnemans,
2015
5 Oil refining Catalyst La, Ce Hydrometallurgy NA Ferella et al. 2016
(Review)
6 NiMH magnets Nd, Sm, Pr, Hydrometallurgy 98.1 (Nd), 95.5 (Sm), 95.5 (Pr), Meshram et al. 2016
Ce 89.4 (Ce)
7 NiMH magnets (Review) La, Nd Hydrometallurgy NA Sinha et al., 2016
8 Permanent Magnet REE Hydro & Pyrometallurgy NA Sun et al., 2016
(Review)
9 Phosphor (lamps) Tb, Eu, Y Mechanical Activation & leaching 89.4 (Tb), 93.1 (Eu), 94.6 (Eu) Tan et al., 2016
10 Fluorescent lamp Eu, Y Hydrometallurgy 99.9 Tunsu et al., 2015
188 T. Dutta et al. / Environmental Research 150 (2016) 182–190

good example of this scenario, recovery of REE oxides (of neody- by the strength of the system (Sprecher et al., 2015).
mium, praseodymium, and dysprosium) has actually been made Key components of the sustainability in the production system
from commercial NdFeB magnets and industrial scrap magnets by and material supply chain include: i) resistance, i.e., the ability to
employing membrane-assisted solvent extraction (MSX: Kim et al., combat the disturbances without any substantial loss of function,
2015). The demonstrated process was capable of selectively re- ii) speed of recovery, and iii) flexibility, i.e., the ability to switch
covering pure REE oxides (e.g., based on the XRD and SEM-EDX between alternative supply systems. According to Binnemans et al.
analysis) from scrap magnets at good yields without any co-ex- (2015), such supply chain resilience in REEs market has been
traction of non-REEs over the 120 h run. achieved either by substituting critical REEs with less critical
It should be noted that although many lab-scale experiments metals or by augmenting the supply by sustainable primary
reported a very high recovery for REEs, full proof recycling tech- mining and recycling. The rapidity of the system response could be
nologies of REEs are still non-existent at industrial-scale (Sun further buttressed by additional interventions from the govern-
et al., 2016). However, nowadays, some chemical and electrical ment and/or other regulatory agencies, as discussed in Section 4.2.
companies are tackling the challenge of developing steps and
processes to recover high purity REEs from wastes. For instance,
the 2013 joint venture between Honda and Japan Metals and 5. Conclusion and recommendations
Chemicals (JMC) explored the use of molten salt electrolytes to
recycle REEs into usable oxides from used nickel-metal hydride REE-based devices and renewable energy technologies are ex-
(NiMH) batteries. Likewise, Umicore and Solvay Rhodia (chemical pected to drive tremendous growth in REE demand. However,
companies) developed a similar initiative (Forbes, 2014). Other there are also critical challenges, because the costs of mining and
multinational corporations have also joined forces in REE recovery, extracting primary REE resources are high. Because richer deposits
e.g., Mitsubishi Electric (recycling REEs from air conditioners) and are highly localized in a limited number of counties, the supply
Veolia Environmental Services (recycling REEs from e-waste and and price of REEs could face tactical monopoly. As such, every
lamps) (Forbes, 2014). Such efforts are critical for the sustainable country needs a constant REE supply to support automobile,
supply of REEs in green energy technologies and smart electronic electronic, and allied industries. Indeed, some REE-consuming
devices. nations have ramped up domestic REE production (e.g., Molycorp
Inc, USA and Lynas Corporation, Australia) to avoid large ex-
4.2. Strategies for promoting the preservation of REEs penditures of REE imports. However, the number of such cases are
still sparse. China still has the maximum control over the entire
Another significant challenge in REE primary mining and re- REE value chain and it has overtaken nearly all developed nations
cycling is the development of effective administrative policies to in the REE industry. Therefore, further domestic investments by all
establish and implement recycling programs at governmental or rare earth-consuming nations in primary mining will be needed to
intergovernmental levels. A low level of community awareness overcome this situation. Perhaps, researchers and industrialists
regarding recycling, lack of recycling design, and collection of can thoroughly analyze China's approaches as a case study to build
scrap products are the major roadblocks (Reck and Graedel, 2012). up on the existing framework. Nevertheless, caution should be
However, some of these limitations have been overcome in the practiced to ensure that the mining approaches adopted by most
recent years. This was also reflected in the recycling forecasts by nations are well backed up by geotechnical survey data for the
Rollat et al. (2016) who projected increased possibilities of re- mine site and adjacent areas to help reduce the possibility of any
cycling by 2020. Altogether, there are a number of possible stra- environmental problems. Nonetheless, it is important to empha-
tegies for preserving primary REE resources (Sprecher et al., 2015; size that a landmark in the REEs industry has been achieved
Yang et al., 2013). These include: i) establishing stringent industrial through successful recovery of REEs (99% purity) from end-of-life
standards and laws for the REE industry, ii) reducing red tape to products (urban mining). Our survey confirmed that, in last few
promote faster system response, iii) centralizing management of years, lab-scale REE recovery has increased sporadically, although
REE resources by eliminating illegal mining, iv) developing in- mature procedures for industrial REE recycling are virtually non-
tegrated REE market pricing and distribution systems, v) en- existent. An integrated approach that considers ecology, resource
couraging investment in environmental programs to combat the management, mining techniques, scale of production, market, and
environmental consequences associated with the REE industry, vi) state legislature needs to be implemented. In future, such recovery
promoting the participation of nations with high annual con- methods need to be implemented at the industrial-scale.
sumption of REEs worldwide, and vii) encouraging REE recycling Exploring alternative commercially viable REE resources, e.g., fly
from enriched waste materials, EoL products, and other under- ash and other waste materials, should also be a major research
utilized resources (e.g., Liu and Diamond, 2005). focus.

4.3. Sustainability of REE material supply chain


Acknowledgments
As mentioned earlier, sudden disruptions in the demand-sup-
ply chain of the critical materials may create serious market vo- This study was supported by a grant from the National Re-
latilities. Such raw material threats took place in Re and Nd mar- search Foundation of Korea (NRF) funded by the Ministry of Edu-
kets in 2008 and 2010, respectively; their material prices sky- cation, Science and Technology (MEST) (No. 2009-0093848). E
rocketed within a span of a few months but geared back to normal Kwon also acknowledges the support made by a National Research
levels in the following months. Sprecher et al. (2015) examined the Foundation of Korea (NRF) Grant funded by the Korean Govern-
case of Nd market crisis of 2010 using an approach based on ment (MSIP) (No. 2914RA1A004893).
market resilience theory combined with market flow analysis.
Socio-economically, any material production system embeds three
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