Article

Cite This: Environ. Sci. Technol. XXXX, XXX, XXX−XXX pubs.acs.org/est

Selective Recovery of Rare Earth Elements from Coal Fly Ash

Leachates Using Liquid Membrane Processes
Ryan C. Smith,*,† Ross K. Taggart,† James C. Hower,‡ Mark R. Wiesner,†
and Heileen Hsu-Kim*,†
†
Department of Civil and Environmental Engineering, Duke University, Durham, North Carolina 27708, United States
‡
Center for Applied Energy Research, University of Kentucky, Lexington, Kentucky 40511, United States
*
S Supporting Information
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ABSTRACT: Coal combustion residues and other geological

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waste materials have been proposed as a resource for rare

earth elements (REEs, herein defined as the 14 stable
lanthanides, yttrium, and scandium). The extraction of REEs
from residues often generate acidified leachates that require
highly selective separation methods to recover the REEs from
other major soluble ions in the leachates. Here, we studied two
liquid membrane processes (liquid emulsion membranes,
LEM, and supported liquid membranes, SLM) and compared
them to standard solvent extraction techniques for selective
recovery and concentration of REEs from a leachate of coal fly
ash. All separation methods involved an organic solution of
di(2-ethylhexyl)phosphoric acid dissolved in kerosene or
mineral oil and an acid strippant solution of 5 M nitric acid for the liquid-based separations. The LEM configuration, which
separated REEs by immersing an acid-in-oil emulsion in the ash leachate, resulted in similar recovery percentages of individual
REEs as the conventional solvent extraction approach. The recovery of REEs in the SLM configuration, which involved the
impregnation of the solvent in a hydrophobic membrane, was slower than the LEM process. However, the SLM process was
notably more selective for the heavy (and higher value) REEs, while the conventional extraction and LEM processes were more
selective for the light REEs. A flux-based model of the extraction processes suggested that recovery rates were limited by REE
affinity for the solvent chelator in the SLM, while the rates of REEs separation via LEM were limited by diffusive mass transfer
across the liquid membrane. Altogether, these results help to identify specific steps in the recovery process that future work
should target in the development of scalable liquid membrane separations for REE recovery.

■ INTRODUCTION
Rare earth elements (REEs) are considered critical materials for
a variety of modern technologies including the consumer
electronics, automotive, energy, and defense industries.1−7 With
the history of an unstable REE global supply market as well as
environmental concerns of conventional REE mining practices,
there exists a need to develop alternate REE sources and
improve upon existing methods of REE production.8−10
Recently, researchers have begun investigating the potential
for coal fly ash, coal residuals, geological and marine brines, and
other waste residues as alternative resources for REEs.11−20 For
example, previous research by our group has shown that the REE
content of coal fly ash is typically greater than average crustal
earth values; however, the enrichment depends on the type of
coal feedstock used to generate the ash. Coal fly ashes from
Appalachian Basin coals were typically greater in REE content
(average 600 mg of REEs per kg ash) relative to fly ashes of other
major coal producing regions in the U.S.21 Within the United
States, over 97 Mt of coal combustion products are created each
year with greater than half being utilized for concrete, drywall,
and other industrial and construction applications, and the
remaining portion being disposed of in ash ponds and landfills.22
Technologies for the extraction and recovery of REEs from
coal fly ash are not well developed, and this knowledge gap
creates a need to understand the feasibility of this alternative
source of REEs. The first step in extraction typically produces a
complex acidic leachate containing total REEs at 0.5−5 mg L−1,
with individual REE concentrations ranging from 0.001 to 1 mg
L−1. The leachate mixture will also comprise other major solutes
including ions of sodium, silicon, aluminum, iron, and calcium in
the range of 100−1000 mg·L−1 in the acid mixture (e.g., typically
diluted HCl or HNO3). Other potential “low grade” feedstocks
(e.g., leachates of mine wastes, geological brines) have similar
levels of matrix complexity.11−20 As such, the 102- to 105-fold
difference in concentrations between individual REE and major
Received: January 24, 2019
Revised: March 22, 2019
Accepted: March 25, 2019
Published: March 25, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.est.9b00539

Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
metal ions poses a considerable challenge for economical
recovery of REEs.
Here, we present work on two different separation processes
that use liquid membranes to recover REEs from ash leachate:
liquid emulsion membranes (LEMs) and supported liquid
membranes (SLMs; Supporting Information Figure S1). Liquid
membrane processes use nonaqueous solvents with dissolved
chelating agents to physically separate the aqueous leachate and
acidic strippant phases while simultaneously recovering REEs.
The aqueous strippant may be stabilized within an emulsion
(LEM process), or the nonaqueous solvent may be impregnated
in a physical membrane (SLM process).23−26 These processes
differ from standard solvent extraction as both REE extraction
and recovery occur in the same step. Moreover, the advantage of
liquid membrane process configurations is they maximize
interfacial area of REE mass transfer while also reducing the
required volumes of nonaqueous solvent and chelating agent.
Previous work by others has demonstrated recovery of
neodymium dissolved from rare earth magnets using supported
liquid membranes.27 However, to our best knowledge no studies
have applied this separation approach for coal ash leachates or
similar low-grade feedstocks of geological origin. For liquid
membrane processes, kerosene or other organic liquids are
normally used for the nonaqueous phase.28,29 However, working
with kerosene presents a hazard and handling issue due to its
flammability such that alternative solvents may be attractive.
The efficacy of less hazardous solvents and cost trade-offs must
be evaluated.
The goal of the research was to investigate the application of
liquid membrane processes for recovering REEs from leachates
of coal fly ash as a representative nontraditional REE resource.
The research examined recovery potential as well as selectivity
for individual REEs. Recoveries of individual REEs were also
compared as a function of LEM and SLM process variables such
as separation time or the type of solvent (kerosene or mineral
oil). Finally, a mathematical model of mass transfer potential in
these systems was developed to better understand rate-limiting
process for REE recovery selectivity.
■
MATERIALS AND METHODS
Kerosene (purum) or mineral oil (white, light) were compared
as the nonaqueous phases for the separation experiments.
Kerosene is often used at the industrial scale for liquid−liquid
separations. Mineral oil presents a reduced hazard of
flammability due in part to its lower volatility. Di-2-ethyl-
hexylphosphoric acid (DEHPA, 97% purity) was dissolved to a
concentration of 10% (v/v) into either kerosene or mineral oil
solvent. DEHPA is a strong metal chelator for REEs that is
frequently used for industrial metal separations and is
considered a less hazardous metal carrier than other industrially
relevant organophosphorus compounds such as tributyl
phosphate.30,31 The acid strippant solution for all separations
comprised of 5 M HNO3 (≥99.999% purity, trace metal basis).
For the liquid emulsion membrane, Span 80, a hydrophobic
surfactant, was used as a stabilizer for the emulsion. All chemicals
were purchased from Sigma-Aldrich and used without further
purification.
Fly Ash Leachate. Leachates were produced from a fly ash
sample collected in 2014 from a storage silo of a coal-fired power
plant in Kentucky. This ash sample was produced from a coal
feedstock originating from the Central Appalachian Basin
region. In a previous study,32 we report that this sample
contained total REE content of 703 mg kg−1 and comprised the
B DOI: 10.1021/acs.est.9b00539
Article
following major metal element composition 54.1% as SiO2,
28.4% Al2O3, 10.9% Fe2O3, and 1.28% Ca (sample ID no. for this
ash is 93938 App-FA1 in previous studies describing REE
chemical speciation and leaching methods).21,32,33
Leachates containing the REEs were produced from this ash
by alkaline roasting followed by acid leaching, a method that is
similar to the previous report.21 In brief, 4 g of fly ash and 4 g of
powdered sodium hydroxide were mixed in a zirconium crucible
and heated at 450 °C for 30 min in a muffle furnace. The roasted
ash was cooled to room temperature and mixed with 1 L of 0.11
M HNO3 for 12 h on a stir plate. After mixing, solids were
allowed to settle for 1 h and the supernatant was decanted from
the remaining solids. For all separation experiments, the
decanted leachate was used within 8 h of preparation.
In addition to the coal ash leachates, the LEM and SLM
separations were tested on a synthetic leachate solution that was
formulated based on the average composition of leachate
solutions generated from four different Appalachian coal fly
ashes (Table S1 in the Supporting Information). The use of a
synthetic solution enabled consistent testing of the methods, as
the alkaline roasting and acid leaching process resulted in some
variation of leachate composition. The synthetic leachate was
prepared by mixing the hydrated nitrate salts of major metals
(Na, Mg, Ca, Al, and Fe ranging from 10 to 6000 mg L−1) and
sodium metasilicate nonahydrate in a solution of HNO3 (5% v/
v). Seven REEs (Sc, Y, Nd, Eu, Tb, Dy, and Er) were added from
their respective standards (Inorganic Ventures) to a final
concentration of 150 μg L−1 each.12 This concentration value is
approximately 1−100 times greater than concentrations in fly
ash leachates. These REEs were selected for initial testing based
on their criticality34 and also to span a spectrum of light,
medium, and heavy REEs. A comparison of individual major
metal and REE concentrations in the real and synthetic leachates
is provided Table S1. Unless otherwise noted, all separation
experiments were performed with real coal ash leachates, as
described above.
Liquid Emulsion Membrane. The LEM process was based
on methods by others23,25,35,36 and entailed first a preparation of
a water-in-oil emulsion. The oil-phase comprised of 10% (v/v)
DEHPA and 1% or 3% (v/v) Span 80 in either kerosene or
mineral oil with a total final oil-phase volume of 50 mL. This oil
phase was combined with 50 mL of 5 M HNO3 stripping
solution, added dropwise under high speed mixing at 7000 rpm
(T18 Ultra-Turrax disperser, IKA Works, Inc.) for a total
volume of 100 mL for the prepared emulsion. Immediately after
preparation, the emulsion was mixed with 500 mL of coal ash
leachate and stirred with a magnetic stir bar at 200 rpm for 15
min to 1 h extraction time. After extraction, the leachate/
emulsion mixture was poured into a 2 L glass separatory funnel,
held static for 2 h, and decanted into separate aqueous and
emulsion phases. After emulsion separation into oil and acid
phases, the acid was analyzed for REE and major ion
concentrations by inductively coupled plasma mass spectrom-
etry (ICP-MS), as described below.
Initial work was first performed using the synthetic leachate to
determine the optimum amount of Span 80 for the kerosene and
mineral oil emulsions. After the surfactant amount was
determined, three separate experiments were performed using
a real ash leachate and mineral oil as the diluent for DEHPA and
Span 80 (2%). Due to the difference in volume between acid
strippant and leachate, the total mass of recovered REEs was
compared to the total mass of initial REEs in the leachate.
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Environmental Science & Technology Article

Figure 1. (A) Average percent recovery (n = 3) of major ions and REEs using solvent extraction with 10% DEHPA (v/v) in kerosene after 24 h
extraction. Error bars indicate standard deviation. (B) Mass recovery via liquid emulsion membrane (at 15, 30, and 60 min mixing time) utilizing liquid
phases of 10% DEHPA and 2% Span 80 in mineral oil, and 5 M HNO3 as the acid strippant. (C) Average percent recovery (n = 3) of major elements
and REEs via supported liquid membrane (SLM) using 10% DEHPA in kerosene from a leachate of coal fly ash after 24 h. Error bars indicate standard
deviation. Bar colors correspond to major ions (blue), REEs (green), and radionuclides (red).

Supported Liquid Membrane. A 10% (v/v) solution of
DEHPA in kerosene or mineral oil was prepared and passed
through a 47 mm 0.22 μm PVDF membrane (EMD Millipore)
by vacuum filtration until the DEHPA solution had soaked
through the entire membrane. PVDF was chosen for the
membrane due to its high hydrophobicity and use by other
researchers.37 The membrane was removed from the vacuum
filtration apparatus and soaked in the remaining 10% DEHPA
mixture at least 12 h. Then the membrane was placed in an H-
cell reactor system (Item # MFC 250.40.0, Adams & Chittenden
Scientific Glass) consisting of two 250 mL flanged glass jars that
allowed placement of the prepared 47 mm membrane between
the two glass chambers (see Figure S2 for a schematic). Ash
leachate and 5 M HNO3 stripping solution (250 mL each) were
added to opposite sides of the H-cell reactor and stirred at 700
rpm. Initial testing with synthetic leachate focused on
determining the optimal amount of time to perform extraction,
and the effect on recovery due to the difference between using
kerosene and mineral oil as the support phase for DEHPA. For
testing with real leachate, only kerosene was used as the diluent
for DEHPA. Triplicate SLM extractions were performed on
replicate aliquots of a fly ash leachate over 24 h; initial studies on
extraction demonstrated equilibrium was reached after 20 h
(Figure S3). The strippant concentration after 24 h was analyzed
for major and trace elements via ICP-MS, as described below.
C DOI: 10.1021/acs.est.9b00539
The concentrations of the triplicate separations were averaged
for each element.
Conventional Solvent Extraction. In addition to the two
liquid membrane processes, standard solvent extraction was also
performed in triplicate using both kerosene and mineral oil at
the same ratios of solvent, acid, and coal ash leachate used for the
liquid emulsion experiments. A 100 mL aliquot of real coal ash
leachate was separately mixed with 10 mL of 10% DEHPA in
mineral oil for 24 h. The organic and aqueous portions were
decanted, and 4 mL of mineral oil was mixed with 4 mL of 5 M
HNO3 for another 24 h and the acid was analyzed for REE
content by ICP-MS.
Elemental Analyses. Major and trace element concen-
trations were analyzed in the leachate feedstocks and separation
products by ICP-MS (7900, Agilent Technologies). Elements
Ca and Si were quantified under hydrogen reaction gas
conditions, while all other elements, including the REEs, were
quantified under helium reaction gas mode. Instrument
calibrations were performed at the start of a sample batch, and
internal standards of Rh and In were spiked in each sample and
used to correct for shifts in signal intensity during a batch run.
Barium oxides are known to contribute to the mass signal for
europium,38,39 and silicon oxides contribute to the mass signal
for scandium.40 Due to the high concentrations of both barium
and silicon in ash digests, it is necessary to account for these
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Table 1. Estimated Composition, on a Dry Mass Basis, for Major Elements and Total REEs in Initial Leachate and Final Strippant
Products of Liquid Emulsion Membrane (LEM), Supported Liquid Membrane (SLM), and Conventional Solvent Extractiona
15 min LEM 30 min LEM 60 min LEM SLM Kerosene Solvent
initial final initial final initial final initial final initial final
leachate strippant leachate strippant leachate strippant leachate strippant leachate strippant
(mg kg−1) (mg kg−1) (mg kg−1) (mg kg−1) (mg· g−1) (mg kg−1) (mg kg−1) (mg kg−1) (mg kg−1) (mg kg−1)
Na 681 000 410 500 754 000 429 200 796 000 402 600 821 000 702 200 753 000 2079
Mg 7500 18 050 3840 8794 7790 16 600 7450 6297 7850 260
Al 132 000 376 700 103 000 442 300 73 700 385 400 57 000 95 200 99 000 966 800
Si 138 000 40 810 108 000 25 700 97 400 32 330 88 600 124 300 103 000 1574
K 11 700 8396 12 300 8056 13 000 8301 14 200 20 870 12 900 176
Ca 9210 130 200 5780 75 570 7920 143 000 7410 26 960 8870 23 270
Fe 19 100 3054 12 000 2660 2480 739 3050 16 220 12 900 1209
REE 302 3300 146 1710 176 3700 136 5280 213 1820
a
Concentrations were calculated by taking the measured aqueous concentrations and assuming the metals formed nitrate salts upon drying. See the
Supporting Information spreadsheet file.

interferences that affect quantitation of Eu and Sc. A detailed
explanation of the method for correction can be found in the
Supporting Information, but in brief, the percent oxide
formation for Ba and Si was calculated and then used to correct
the signal intensity at 153 and 45 m/z (mass/charge) for Eu and
Sc, respectively.
Separation Factor for Individual Metals. For each
process, the relative separation efficiency for each REE was
quantified by computing individual distribution coefficients for
each element and comparing this distribution to a reference
metal. Here, we defined the distribution coefficient of a
particular metal, D Me , as the ratio between the final
concentration in the strippant, [Me]strippant, over the final
concentration remaining in the leachate after extraction,
[Me]leachate:
[Me]strippant
DMe =
[Me]leachate
Previous work by Kim et. al using the SLM process to recover
REEs from scrap magnets using TODGA, showed distribution
coefficients for Nd on the order of 103.27 Due to the complex
nature of the coal ash leachate, we compared the relative
selectivity of a particular metal to a reference metal, sodium
(Na), by calculating an apparent separation factor, αMe/Na
according to
DMe [Me]strippant [Na]leachate
αMe/Na = =
D Na [Na]strippant [Me]leachate
Values for αMe/Na were calculated for each REE as well as for
major ions (Ca, Fe, and Al). These calculations utilized the
following resulting data for each process: (1) the average of
triplicate extractions in the conventional solvent, (2) the 30 min
mixing time (n = 1) for the LEM process, and (3) the average (n
= 3) at the 24 h time point for the SLM process. Na was used as
the reference because this metal was the greatest concentration
for all dissolved metals in the ash leachate feedstock.
substantial mass recovery of Al and Ca was observed (64% and
17%, respectively). However, radioactive elements such as Th or
U were not recovered to appreciable extents. Note that the
percentage for each element refers to the final element mass in
the acid stipping solution normalized to the element mass in the
initial feed solution (e.g., the ash leachate). Concentrations
values for major ions and REEs for the feed and the strippant
product solutions are provided in the SI .xlsx data file.
While the percentage recovery provides information for
individual elements, the purity of the mixed REE product is
easier to compare to REE extraction technologies by calculating
a dry mass-based concentration. To estimate this concentration,
we used the measured aqueous concentrations of all measured
metal and metalloid elements (REEs and major cations) in the
strippant and determined the dry mass assuming all metal
cations formed nitrate salts upon drying (e.g., La(NO3)3). Si and
U were assumed to dry as H4SiO4 and UO2(NO3)2, respectively.
(1) For the solvent extraction data, the mixed REE purity was
estimated to be 1820 mg·kg−1 (dry mass basis), an 8-fold
increase compared to the initial leachate (Table 1).
Liquid Emulsion Membrane Processes. The LEM
separation process was first tested on a synthetic leachate to
establish surfactant concentrations necessary to form a stable
emulsion while also maximize REE separation. We observed a
decrease in REE recovery when the surfactant concentration
increased from 1% to 3% in mineral oil (Figure S4). An excess of
surfactant at the oil−water interface might hinder transport of
(2)
REEs into the oil phase, as indicated by others.23 We also
observed that increasing the concentration of Span 80 improved
the stability of the emulsion. LEM separations using less than 2%
Span 80 did not yield an emulsion that could be stable over for a
60 min reaction and 2 h settling time. Therefore, 2% Span 80 was
selected for all subsequent experiments with real ash leachates as
a means to maximize both emulsion stability and REE recovery.
The recovery percentages of REE from the coal ash leachates
by the LEM process were similar to results of the conventional
solvent extraction process (Figure 1B). We note that the LEM

■ RESULTS AND DISCUSSION

Conventional Solvent Extraction. The separation and
recovery of REEs from the leachates via conventional solvent
extraction (with kerosene and DEHPA) varied with the type of
REE. The recovery percentages for the lighter REEs (La, Pr, Nd,
Sm, and Eu) were generally greater than heavier REEs (Dy, Ho,
Er, Tm, Yb, and Lu; Figure 1A). In addition to the REEs,
D DOI: 10.1021/acs.est.9b00539
separation utilized mineral oil as the organic solvent for the
DEHPA (10% v/v) instead of kerosene with DEHPA.
Regardless, the general trend of greater extraction of the light
REEs over the heavy REEs was observed in the LEM process.
The mixing time of the LEM process varied between 15, 30,
and 60 min with a constant phase separation time of 2 h.
Between mixing times for the LEM process, a 60 min extraction
time achieved greater than 70% recovery of most REEs, and as
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology Article

the mixing time increased individual recoveries approached the Difficulties with recovering Sc after extraction with DEHPA
recoveries observed with solvent extraction with kerosene, have been known by others for almost 50 years.42 If these
Figure 1B. For all REEs, there was little difference between 15 processes are to be scaled up, economical solutions must be
and 30 min extraction, but a large difference between 30 and 60 developed for recovering Sc and other heavy REEs from the
min extraction. This difference is especially true for most heavy extractant in order to prevent eventual poisoning of the DEHPA.
elements such as Tb, Dy, and Ho that increased from 60%−66% Separation Factors for REE and Major Metal Ions. In
recovery at 15 min extraction to 77%−83% recovery for 60 min comparing the three processes, we observed two important
extraction. Interestingly, the recoveries of Ca and Al switched distinctions: selectivity trends between individual REEs and
between solvent extraction and LEM with Al being recovered selectivity of the REE relative to other competing metals such as
more effectively using kerosene solvent extraction and Ca Ca, Fe, or Al. The apparent separation factors αMe/Na of each
recoveries relatively greater for the mineral oil LEM. REE in the kerosene solvent extraction were always greater than
The expected dry mass REE contents of the LEM product respective αMe/Na values for either liquid membrane processes
were approximately 3300, 1710, and 3700 mg kg−1 for 15, 30, due to the low recovery of Na during solvent extraction (Figure
and 60 min mixing times (Table 1). These values represent a 10-, 2A). The αMe/Na values for the solvent extraction also tended to
12-, and 21-fold increase in purity relative to the initial feed REE
concentrations. For the 15 and 60 min mixing times, REE purity
was almost double the dry mass purity for the kerosene solvent
extraction (1820 mg kg−1.).
Supported Liquid Membrane Process. Initial studies
were performed with the synthetic leachate to understand the
time scale of the SLM process. The results (Figure S3) showed
that the concentrations of REEs in the acid strippant increased
within the first 3 h of separation and, after this period, did not
change considerably between the 3 and 20 h. Based on these
results, we used the 24 h time point to represent an approximate
steady state for subsequent SLM experiments with real coal ash
leachate solutions.
The application of the SLM system for the coal fly ash
leachates resulted in relatively higher percentage recoveries for
the heavy REEs compared to the light REEs (Figure 1C). For
example, the recoveries of Y, Tb, Dy, Ho, Er, Tm, Yb, and Lu
were all greater than 75% after 24 h of extraction, while recovery
of La, Ce, Pr, and Nd was less than 50%. This general difference
between the light and heavy REEs is opposite to the trend
observed for the LEM and conventional solvent extraction
separations. For the major metal constituents Na, Mg, Al, Si, K,
Ca, and Fe, less than 10% was recovered in the strippant
solution. When comparing the expected solid phase product
between the all recovery processes studied (Table 1), the SLM
process resulted in the highest purity with 5280 mg kg−1 total
REEs. The expected solid phase REE content of the original
leachate was only 136 mg kg−1 indicating that the SLM process Figure 2. Selectivity values for kerosene solvent extraction, LEM
was capable of increasing REE content by approximately 39 process, and SLM process for (top) all REEs and (bottom) major
competing metals and light and heavy REEs.
times. Between all three studied processes, the SLM process
provided the highest purity mixed REE product.
However, in addition to the desired REEs, high recovery of decrease slightly with increasing hydrated ionic radius for the
uranium was also observed. Uranium is commonly extracted REE. The LEM αMe/Na values remained fairly constant with
during nuclear fuel reprocessing using tributyl phosphate which increasing hydrated ionic radius apart from Ce, Yb, and Lu while
is similar to the extractant DEHPA used in this study.31 While αMe/Na values for the SLM process increased with ionic radius.
the total recovery was 75%, the expected amount of uranium in In comparisons of the REEs to major competing metals,
the final dried product only would be 0.39% (see the Supporting different trends emerged where the LEM and SLM processes
Information). always show greater selectivity for REEs when compared with
Low Recovery of Scandium. For all three liquid separation solvent extraction, Figure 2B. All three processes demonstrated
processes, Sc was not observed in appreciable concentrations in greater selectivity for REEs over Ca and Fe, but αMe/Na values for
the final acid strippant solution. For example, we observed that Al during solvent extraction were within the same order of
in the SLM process the Sc concentration in the leachate feed magnitude as the light REE Nd. In total, while the αMe/Na values
decreased from an average 29 to 19 μg/L, indicating that 32% of for REEs during solvent extraction were consistently higher than
the original Sc was lost from the leachate but only 1% was both the LEM and SLM processes, compared to other major
recovered into the strippant. The Sc complex with DEHPA has a competing metals like Al, the LEM and SLM processes
very high stability constant (relative to the other REEs). For demonstrated higher selectivity for REEs
example, the estimated binding constant K for the reaction Me3+ Difference between Kerosene and Mineral Oil. The
+ 3 DEHPA2 + Me(DEHP·DEHPA)3 + 3H+ is 1.1 × 107 for Sc3+ importance of the carrier organic solvent for the liquid
(see the Supporting Information) and 1.8 × 103 for Dy3+.41 membrane processes was further explored by directly comparing
E DOI: 10.1021/acs.est.9b00539
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Environmental Science & Technology Article

Figure 3. Effect of solvent on recovery of selected elements using synthetic leachate for (left) liquid emulsion membrane process with 30 min mixing
time (n = 1) and (right) supported liquid membrane processes after 20 h equilibration time (n = 1). Note that REE separation from real leachate with
the mineral oil solvent was not reproducible.

kerosene and mineral oil for separation of REE in synthetic coal

ash leachates. In the LEM process, the recovery of the REEs (Y,
Nd, Eu, Tb, Dy, and Er) was greater in mineral oil than with
kerosene as the organic solvent (Figure 3A). In contrast, the
SLM process demonstrated a consistently lower recovery using
mineral oil as a solvent (Figure 3B). This difference in recoveries
was approximately 18% for each REE in the case with 1% Span-
80 as the surfactant. For the SLM system, the opposite effect of
solvent was observed, with kerosene providing REE recovery
percentages that were an average 16% greater than REE recovery
percentages in the mineral oil SLM system. Previous work by
others43 with an amide chelating agent also has demonstrated
the impact of solvent on REE recovery. While mineral oil and
kerosene are both hydrocarbon mixtures, they may be
sufficiently different in polarity, resulting in observable variation
in REE mass transfer of the DEHP−metal complex.43 We also
note that we had significant difficulty in reproducing the mineral Figure 4. (A) Schematic of reactions during the separation and
concentration of REEs from coal fly ash leachate in the liquid emulsion
oil/DEHPA system for the SLM process. Despite using the same
membrane and the supported liquid membrane processes. (B)
experimental conditions, we sometimes observed zero recovery Concentration profile of a single REE (purple line) for a transport
of REEs (data not shown). The SLM separations with kerosene model where the steady state flux of the metal across each liquid (JL, JO,
were fairly reproducible (e.g., Figure 1C). While the reason for and JS) was controlled by diffusive transport across a diffusion film layer
the poor reproducibility of mineral oil in the SLM system of thickness δ at each liquid−liquid interface.
remains to be elucidated, we suspect that the miscibility of the
DEHPA in mineral oil might be a factor.
Model of REE Flux for Liquid Membrane Processes. strippant phases, the thickness of the oil layer for mass transfer,
The relative recovery of individual REEs differed greatly and the concentration of available chelating agent.
between the LEM and SLM processes. The lighter REEs tended In order to identify the potential influences of the system
configuration on overall recovery of different REEs, we
to be recovered more efficiently in the LEM process, while the
calculated the potential flux of each REE under steady state
heavier REEs were more efficiently extracted during the SLM
conditions as a means to understand the major rate-limiting step
process even though both processes used similar liquid−liquid for mass transfer. The model assumed that REE transport
reagents (10% DEHPA in organic solvent and 5 M nitric acid as occurred through five regimes: (i) bulk leachate, (ii) leachate
the strippant). The transfer of REE ions from the original ash film, (iii) organic phase, (iv) strippant film, and (v) bulk
leachate, into the oil phase and then into the acid stripping phase strippant as detailed in Figure 4B. The calculations were
entailed a multiple-step process (Figure 4A) including: (1) loss performed with the following assumptions:
of hydration shell surrounding the trivalent rare earth ion, (2)
1 Each flux (JL, JO, and JS) represents the flux of an
complexation of the rare earth ion with DEHPA, a process that individual metal.
depends on the relative binding constant between the metal ion 2 At steady state, the flux across the boundary layer of each
and the ligand, (3) mass transfer of the metal−DEHPA complex phase is equal (JL = JO = JS) and was equal to the product
through the oil phase, a process driven by diffusive flux across a of a diffusion coefficient and a concentration gradient
concentration gradient in the oil phase, (4) release of rare earth (Fick’s first law).
ion at the interface of the acid stripping solution and proton 3 The concentration of the fully protonated DEHPA in the
exchange with Me(DEHP·DEHPA)3, and (5) back diffusion of organic phase, (HR)2, is determined by equilibrium
protonated DEHPA to the oil-leachate interface. Any one of between the leachate and the organic phase.
these steps might be rate limiting for REE ion recovery in the 4 After extraction by DEHPA, all metals are then recovered
acid stripping step, depending on system configurations such as by the acid strippant with no metals remaining in the
interfacial surface areas between the leachate-oil and oil- organic phase.
F DOI: 10.1021/acs.est.9b00539
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology Article

5 The concentration of acid in the strippant phase remains (HR)2, the diffusion boundary layer thickness (δL, δO, and δS),
constant (5 M). and the diffusion coefficients DL, DO, and DS in the leachate, oil,
Complexation of all metals with DEHPA was assumed to and strippant phases. A complete summary of the methods used
occur according the following equilibrium reaction: to determine each individual parameter is given in the
Supporting Information.
Me3 + + 3(HR)2 ↔ Me(R·HR)3 + 3H+ (1′) Model calculations (Figure 5A) suggest that the flux of each
metal varies with the configuration of the system (i.e., LEM or
where the overbar indicates the organic solvent phase. DEHPA
dissolved in nonaqueous solvent exists as a dimer, (HR)2, and
the lanthanide−DEHPA complex exists as one lanthanide ion
with three DEHPA dimers, [Me(R·HR)3].44,45 For each
lanthanide, there is an associated equilibrium constant:
[Me(R· HR)3 ][H+]3
Keq = 3
[(HR)2 ] [Me3 +] (2′)
Equation 2 can be rearranged to create a relationship between
the metal concentrations at the interfacial regions of the organic
phase and both aqueous phases:
3
[Me(R· HR)3 ] Keq[(HR)2 ]
kL = =
[Me3 +]L [H+]L
3
(3a)
3
[Me(R· HR)3 ] Keq[(HR)2 ]
kS = =
[Me3 +]S [H+]S
3
(3b)
where subscripts L and S indicate the leachate and strippant
phases, respectively. The flux of an individual metal ion through
each phase is assumed to be driven by gradients in concentration
C as described by Fick’s First Law:
DL B Figure 5. Predicted initial fluxes for individual metal ions (normalized
JL = (C L − C LF) to the initial concentration in the leachate) for (A) both liquid
δL (4a)
membrane processes for a leachate with pH 4 (note log scale) and (B)
DO F the LEM process (same data points as part A) showing small variation
F
JO = (CO,L − CO,S) in flux due to differences in diffusion coefficients.
δO (4b)
DS F
JS = (CS − CSB) SLM), its ionic radius, and its binding affinity with DEHPA (i.e.,
δS (4c) Keq). The most important difference between the two systems is
the value for [(HR)2] within the organic phase. For the LEM
where the subscripts L, O, and S indicate the parameters for the
system at initial leachate pH 4, the calculated concentration of
leachate, organic, and strippant phases, respectively, and the
(HR)2 was 0.141 M, resulting in the following value for kL
superscripts B and F indicate the bulk and film layers,
(according to eq 3a′):
respectively. The diffusion coefficients D were calculated from
the hydrated ionic radius according to the Stokes−Einstein 3
[Me(R· HR)3 ] Keq[(HR)2 ]
relationship (Supporting Information). The diffusion film layer kL = =
δL and δS in the leachate and strippant phases were calculated [Me3 +]L [H+]L
3

from the mixing speed while δO was based on microscopic Keq(0.1410.141M)3

observations of oil film thickness in the emulsion or reported = = 2.81 × 109Keq
membrane thickness for the SLM system (Supporting (10−4)3 (3a′)
Information).
As a result of this (HR)2 concentration, at pH 4, the term kL is
By assuming that JL = JO = JS and using eqs 3a and 3b, an
approximately 109 or greater, depending on the value of Keq.
overall expression for the flux of an individual metal ion
normalized to its bulk concentration in the leachate can be Therefore, the kLδ L term in the denominator of eq 5 is
DL
expressed as δO k SδS
significantly greater than the and terms, resulting in the
DO DS
J kL
= following simplification:
C BL kLδ L
+
δO
+
k SδS
DL DO DS (5) kLδ L δ kδ J k D
for ≫ O and S S , L
= k δL = L
+ + DL DO DS CB δL
The variables kL and kS depend on [H ]L and [H ]S, respectively, L L
DL (6)
and both depend on the unchelated DEHPA concentration
[(HR)2]. Therefore, the normalized flux shown in eq 5 depends This simplification for the LEM system implies that normalized
on nine variables: the pH of the leachate and strippant phases fluxes for the REEs were limited by diffusion through the
(i.e., [H+]L and [H+]S), concentration of free chelating agent leachate film. The lanthanide contraction results in a decrease in
G DOI: 10.1021/acs.est.9b00539
Environ. Sci. Technol. XXXX, XXX, XXX−XXX
Environmental Science & Technology
ionic radius with increase in atomic number along the lanthanide
series resulting in an increase in hydrated ionic radius and a
decrease of the diffusion coefficient. The diffusion coefficients
along the lanthanide series were calculated to fall within an order
of magnitude of each other and, therefore, yielded relatively
small differences between fluxes among REEs (Figure 5B) that
was not sufficient to explain the observed results. A likely reason
for this inconsistency is the model assumption of equal fluxes
across all three phases, an assumption that would not account for
observations of certain REE (e.g., Sc or Lu) immobilized on the
organic phase and not recovered by the strippant phase as the
equilibrium constant for Lu is 5 orders of magnitude larger than
La. Thus in the LEM system, diffusion into the organic phase
may be the overall rate-limiting step for the recovery of light
REEs and dissociation of the Me(R·HR)3 complex may be rate-
limiting for the heavy REEs.
For the SLM system, the predicted concentration of (HR)2 at
pH 4 was 9.9 × 10−6 M resulting in kL = 9.7 × 10−4 Keq. As a
consequence, the δO term was the largest term in the
DO
denominator of eq 5 and flux simplified to the following:
δO kδ kδ
for ≫ L L and S S ,
DO DL DS
KeqDO[(HR)2 ]3
J kL kLDO
= = =
C BL δO
δO δO[H+]3
DO (7)
From this simplification, differences in flux between the REEs in
the SLM system could be explained by variations in both the
metal-DEHPA binding constant, Keq, and the diffusion
coefficient DO. The value of DO decreases with increasing
ionic radius (i.e., from light to heavy REE); however, the range
of values are within 1 order of magnitude. In contrast, the value
of Keq increases by 5 orders of magnitude along the lanthanide
series. These results indicate the DEHPA concentration
[(HR)2] is smaller in the SLM system than the LEM, and that
REE competition for (HR)2 is the key factor affecting recovery
and flux in the SLM system. The limiting amount of free (HR)2
is a direct result of the small total volume of solvent present in
the membrane. As such, affinity toward free (HR)2 will be the
deciding factor for overall flux favoring heavier REEs over lighter
REEs.
While the flux calculations can compare the REEs for their
recovery potential, the model inadequately predicts observa-
tions of certain metals. For example, the model indicates a high
flux of Sc. However, in our LEM and SLM separations, we
observed less than 1% of the original Sc in the strippant phase,
and a minimum of 40% Sc remaining in the original leachate
depending on the method of recovery used. Sc was likely
immobilized in the organic phase, probably because of the
strong binding affinity with DEHPA.42
Implications and Future Work. The unique chemical
properties of REEs make them both critical and irreplaceable in
industrial applications. Due to the difficulty and environmental
impact of REE mining, developing methods for the recovery and
concentration of REEs from alternate sources such as coal ash is
crucial. Compared to the conventional kerosene-based solvent
extraction, the LEM process was shown to be a potential
alternative that could be implemented with mineral oil, a less
hazardous solvent than kerosene. Using the developed model,
we demonstrated that the recovery rates of REEs appeared to be
controlled by diffusional mass transfer of the REE across the oil
H DOI: 10.1021/acs.est.9b00539
Article
phase. For the SLM process, total volume requirements for the
organic solvent phase was orders of magnitude lower than
conventional solvent extraction. Thus, REE recovery rate
depended mostly on relative affinity for the solvent carrier
(e.g., DEHPA). These findings are informative for future
investigations of LEM or SLM processes that could focus on
these components of the separation process through exper-
imentation with different chelating agents and the organic
diluents.
Both LEM and SLM processes demonstrate high separation
factors for the REEs in the presence of other competing metal
ion species. Future work should focus on further purification and
recovery of REEs from the strippant solutions in addition to
reducing the total acid requirements. Full scale application of
these processes will also require an understanding the effects of
pH for both leachate and strippant solution on REE recovery.
While this work was focused on leachates of coal fly ash, our
findings are applicable to other dilute mixed metal waste
streams. Future work could focus on applying these methods to
other secondary feedstocks such as acid mine drainage,
geothermal brines, medical/laboratory wastewater, or seawater.
These brine mixtures all pose similar challenges to coal ash
leachates in relation to matrix and difficulty in recovering REEs,
and liquid membrane processes could be advantageous due to
the relatively high selectivity for REE.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.est.9b00539.
Schematic of the LEM and SLM processes, a table of the
four coal ash sinters used as a basis for the synthetic
leachate recipe, schematic of the SLM system, kinetics of
SLM process, methods for correction of ICP-MS analysis,
method estimation of the solid phase composition of the
strippant after evaporation, effect of solvent choice on
LEM process, and the methods used to estimate the
parameters for the flux model (PDF)
Spreadsheet of the initial and final concentrations of
leachate and strippant for all processes (XLSX)
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: rs391@duke.edu.
*E-mail: hsukim@duke.edu.
ORCID
Ryan C. Smith: 0000-0003-2591-416X
James C. Hower: 0000-0003-4694-2776
Mark R. Wiesner: 0000-0001-7152-7852
Heileen Hsu-Kim: 0000-0003-0675-4308
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the U.S. National Science
Foundation (No. CBET-1510965 and CBET-1510861) and
the U.S. Department of Energy (DE-FE0026952).
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J DOI: 10.1021/acs.est.9b00539
Environ. Sci. Technol. XXXX, XXX, XXX−XXX