Minerals Engineering 132 (2019) 169–174

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

Production of a rare earths concentrate after phosphogypsum treatment with T

dietary NaCl and Na2CO3 solutions☆
⁎
Ines Hammas-Nasria, , Karima Horchani-Naifera, Mokhtar Férida, Donatella Barcab
a
Laboratory of Physical Chemistry of Mineral Materials and Their Applications, National Research Center in Materials Sciences, Technopole Borj Cedria B.P. 73, 8027
Soliman, Tunisia
b
Department of Biology, Ecology and Earth Sciences, University of Calabria, Via Ponte Bucci, Cubo 12B, 87036 Arcavacata di Rende (CS), Italy

A R T I C LE I N FO A B S T R A C T

Keywords: Due to their unique physicochemical properties, rare earth elements (REEs) are increasingly becoming sig-
Phosphogypsum nificant in developing new technologies. Their extraction from ores and industrial wastes has attracted the
Enrichment interest of several researchers. Phosphogypsum (PG) is one of many industrial wastes considered as an attractive
Rare earth elements source of such elements. Since rare earths are present in small quantities in PG, the different steps of their
Recrystallized Na2CO3
concentration in this waste remain essential before any attempt of extraction. In the present work, after de-
termining the content of REEs and their distribution in the phosphogypsum sample, a total rare earth enrichment
of about 84% was achieved in the final solid. The method consists of a washing step with 25 g/L sodium chloride
solution followed by leaching the residue with sodium carbonate solution at 90 °C for 1 h. A new result was
discovered while examining the recrystallized Na2CO3 from the carbonated filtrate (at low temperature) with
photoluminescence technique. This analysis shows the characteristic emissions of Ce3+ and Eu3+ at 374 nm and
555–612 nm respectively after selective excitations. The presence of REEs both in the final residue and in the
solid recrystallized from the filtrate suggests that such elements are linked differently in the PG sample.

1. Introduction of calcium fluorophosphate ores by reaction with sulfuric acid in an

In a few years, rare earths have become important elements because
of the originality of their properties and the specific applications that
can be drawn from them in advanced techniques. Their global demand
is steeply increasing (47% increase from 2013 to 2014) (Humphries,
2013; Mishra and Anderson, 2014) and some of them are expected to be
in short supply in the next 15 years (Al-Thyabat and Zhang, 2015). The
main REE-containing minerals which have been successfully used for
REEs extraction are bastnasite, monazite and xenotime. Generally, the
extraction process from such minerals includes a concentration step (by
flotation, gravity and magnetic techniques) allowing the generation of a
REEs concentrate (Sadri et al., 2017). Then, hydrometallurgical
methods are performed on the latter in order to extract REEs.
Due to the global sourcing challenges and the volatile price of REEs,
some researchers are oriented to rare earths recovery from industrial
wastes. This is considered as an interesting alternative, especially for
countries which suffer from pollution problems and which do not have
natural reserves of such elements (like Tunisia). Phosphogypsum, the
solid waste of hydrated calcium sulfate produced during the treatment
aqueous medium, is one of such attractive secondary source of rare
earths. Worldwide, around 7 billion tons of PG have been produced to
date at a current growth rate of 150–200 million tons per annum. In
total, an estimated 21 million tons of REEs are locked in PG waste
dumps around the world (Yahorava et al., 2016). Thus, taking into
account their enormous rejected quantities, the PG can be reused to
recover a significant amount of rare earth elements. This allows con-
suming waste dumps generated for years that have become a serious
environmental nuisance in addition to obtaining high added value
elements such as rare earths.
For extraction purposes, many studies have focused on phospho-
gypsum leaching with sulfuric, nitric, chlorhydric acid as well as mix-
tures of acids and this in order to perform a maximized solubilization of
rare earth elements (Germeau et al., 2013; Habashi, 1985; Hammas-
Nasri et al., 2016; Jarosinski et al., 1993; Preston et al., 1996;
Walawalkar et al., 2016). But in this case the recovery step will be
delicate due to the presence of several troublesome impurities dissolved
in the same acid solution. By analogy with extraction processes from
ores, and since rare earths are in small quantities, one alternative is to

☆
Foundation item: Project supported by the Ministry of Higher Education and Scientific Research of Tunisia.
⁎
Corresponding author.
E-mail address: ines_hammas@yahoo.fr (I. Hammas-Nasri).

https://doi.org/10.1016/j.mineng.2018.12.013
Received 20 June 2018; Received in revised form 2 December 2018; Accepted 5 December 2018
0892-6875/ © 2018 Elsevier Ltd. All rights reserved.
I. Hammas-Nasri et al.
first treat the phosphogypsum to minimize impurities in order to obtain
a rare earths concentrate before the extraction step. In a previous work,
we have shown that the Tunisian PG exhibits better solubility in a 25 g/
L NaCl solution (Hammas et al., 2013a). Thus the main aim herein is to
obtain a REEs concentrate from Tunisian phosphogypsum waste. The
current work consists of treating the sample with dietary NaCl –
Na2CO3 solutions and tracking rare earth elements by ICP-MS and
photoluminescence techniques after each step of the method.
2. Materials and methods
2.1. Materials
The PG studied in this work is an old sample (over 50 years) having
as origin Sfax (Tunisia) stockpiles. It was previously characterized by
different analytical techniques which allowed concluding that it cor-
responds mainly to the CaSO4·2H2O phase with the presence of several
impurities (residual acids (HPO42−), fluorosilicates (SiF62−), Al3+,
Mg2+, Cd2+, Zn2+, Mn2+) (Hammas et al., 2013a, 2013b).
For economic reasons, the sodium chloride solution used in the
method is a dietary salt dissolved in water. Also, the used sodium
carbonate is of high purity (99.5%) produced by “Oxford Lab Chem”.
2.2. Washing step
A phosphogypsum quantity of 500 g was washed with a salt solution
(25 g/L) such that the liquid-to-solid weight ratio was 200. The mixture
was stirred for 10 min to ensure a better solubilization of impurities in
the solution.
2.3. Leaching step
After solid/liquid separation, the wash residue (RI) was leached
with Na2CO3 solution (60 g/L) at 90 °C for 1 h with continuous stirring.
The solid-to-liquid weight ratio was 1/6 and the solution had a pH of
10.8. The filtration leaded to recover the final residue (RF) which was
dried at 50 °C. The carbonated filtrate (FC) was kept at a low tem-
perature (0 °C). Fig. 1 describes the method carried out in this work.
2.4. Infrared spectroscopy
Infrared spectra were performed on a FT-IR System Perkin Elmer
spectrometer using KBr pellets in the region of 4000–400 cm−1. All the
pellets were prepared in the same conditions (KBr mass, sample mass
and pressure).
2.5. X-ray diffraction analysis
The mineral compositions of the obtained residues were determined
by the XRD technique which was carried out by Bruker X-ray dif-
fractometer with Cu-K α1 radiation (Kα = 1.5418 Å). Data were col-
lected in the 2θ range of 5–80° with a step size of 0.01536° 2θ. The
X’Pert HighScore Plus was used as a library database for phases
Fig. 1. Description of the rare earths concentration method.
170
Minerals Engineering 132 (2019) 169–174
identification.
2.6. ICP-MS analysis
ICP-MS analyses were performed at the Department of Biology,
Ecology and Earth Sciences, University of Calabria, Italy. The samples
were powdered in an agate mortar and then dissolved by microwave
digestion using a Mars5 microwave apparatus (CEM technologies).
About 100 mg ( ± 0.01 mg) of each powder was placed in a microwave
vessel with a mixture of Merck “suprapur” quality hydrofluoric acid
(6 ml HF), nitric acid (5 ml HNO3) and perchloric acid (3 ml HClO4),
covered and sealed with a cap and subjected to an oven method that
consisted of a 15 min ramp to 200 °C and a pressure of 600 PSI, then
held at temperature for 15 min and then a 15 min cool down. Unclear
solutions containing some residues were obtained. The content of each
vessel was allowed to heat up to 200 °C. Before the complete eva-
poration of acid, we added 3 ml of pure HClO4 and we maintained
heating up to 200 °C. Before the complete evaporation, 5 ml of HNO3
(5%) was then added. Clear and colorless solutions were finally ob-
tained. These latter, were left to cool down gently and made up to a
standard volume in a 100 ml volumetric flask with Millipore water in
order to prepare the mother solutions. External calibration curves were
prepared using Perkin Elmer “multi-element Calibration Standard 2
solution” to analyze rare earth elements. Standard reference materials
Micaschist (SDC1) were prepared in the same way and were used as
unknown samples during the analytical sequence. Concentrations of the
elements were compared with certified values to evaluate accuracy and
precision of analytical data (Mastandrea et al., 2010).
2.7. Photoluminescence measurements
Photoluminescence measurements were recorded on samples pellets
with Perkin Elmer spectrometer LS55. All the pellets were prepared in
the same conditions (mass, pressure) in order to allow a reliable com-
parison of emission intensities. In the case of the carbonate filtrate, the
analysis was carried out using a quartz tank containing the solution in
question.
3. Results
3.1. Content and distribution of rare earths in the raw PG sample:
Since we are interested herein to trace elements and precisely in
rare earths, ICP-MS analysis was carried on the PG sample in order to
determine its initial rare earths content. The results, summarized in
Table 1, show a total rare earths content of about 350 ppm.
Then, ICP-MS analysis was carried out on the different fractions
obtained after sieves separation. The results of the particle size dis-
tribution of the phosphogypsum as well as rare earths content in each
fraction are summarized respectively in Figs. 2 and 3. As rare earths
were distributed homogenously in the different fractions, it was decided
not to use granulometric separation in sample preparation.
I. Hammas-Nasri et al. Minerals Engineering 132 (2019) 169–174

Table 1 the leach residue (RF) were quartz (reference code 01-083-2466), calcite
Rare earths content in the raw Tunisian phosphogypsum (CaCO3) (reference code 01-072-1937) and sodium carbonate sulfate
determined by ICP-MS analysis. Na6(SO4)(CO3, SO4) (reference code 00-024-1134).
Element Content (ppm)
3.3. REE’s content in residues
Y 80.81
La 54.42
Ce 96.73 The aim of the described method is to solubilize the maximum
Pr 12.71 amount of water soluble impurities while leaving the rare earths intact
Nd 59.42 in the calcium sulfate matrix.
Sm 9.63
By mass calculation, phosphogypsum’s washing with the salt solu-
Eu 2.29
Gd 9.55 tion made it possible to eliminate 86% of impurities. ICP/MS results
Tb 1.46 showed an enrichment of rare earths in the order of 81% in the inter-
Dy 8.94 mediate residue RI. Furthermore, treatment with the carbonated solu-
Ho 1.81 tion allowed not only to reduce the residue grain size, but also to
Er 5.47
Tm 0.71
eliminate additional impurities, improving thus the rare earths en-
Yb 5.61 richment to 84%. The results of the ICP/MS analysis performed on both
Lu 0.65 residues (RI) and (RF) are summarized in Table 2. This table also shows
Total REE content 350.21 the total enrichment of each rare earth element which was calculated as
follows:

30.7 % (REE(RF ) − REE(PG) )

Total REE enrichment (%) = × 100
30 REE(RF )

25
22.28 % 3.4. Analysis of the carbonated filtrate
20
Distribution (%)

By examining the carbonated solution which was kept at low tem-

15 14.21 %
11.13 %
10.66 % 9.81 %
10
5
1.21 %
0 bonate recrystallization showed that it is free of luminescent elements
53-80 80-100 100-180 180-300 300-600 600-1000 1000<
Particle size ( m)
Fig. 2. Particle size distribution in aged Tunisian PG.
3.2. Residues characterization
The obtained residues were analyzed by infrared spectroscopy and
X-ray diffraction. The superposition of residues (RI and RF) infrared
spectra with that of the raw PG is displayed in Fig. 4. After washing the
phosphogypsum with the salt solution, the (RI) residue spectrum
showed a decrease in sulfate vibrations intensities in 1200–1100 cm−1
and 700–600 cm−1 regions with shrinkage of water stretching vibra-
tions in the 3700–3200 cm−1 region. Also, the band at 837 cm−1,
corresponding to H2PO41− and HPO42− initially syncrystallized with
phosphogypsum, have disappeared in the (RI) spectrum. Moreover,
leaching with the carbonated solution led to the appearance of new
bonds around 1400 cm−1 and 870 cm−1 in the RF spectrum. Such vi-
brations correspond respectively to the ν3 (as) (CO) stretching modes
and the δ (OCO) out of plane bending modes of carbonate compounds.
In a previous work (Hammas et al., 2013b), the characterization by
X-ray diffraction of the same PG sample used herein showed the pre-
sence of ardealite Ca2(HPO4)(SO4)(H2O)4, brushite CaHPO4·2H2O and
malladrite Na2SiF6 phases as impurities in the major gypsum phase
CaSO4·2H2O The XRD pattern of the wash residue (RI) consists mainly
of hemihydrated calcium sulfate CaSO4·0.5H2O (reference code 01-081-
1848) with the co-existence of secondary phases which were identified
to dihydrated calcium sulfate CaSO4·2H2O (reference code 01-074-
1433), sodium chloride NaCl (reference code 01-078-0751) and quartz
SiO2 (reference code 01-083-2466) (see Fig. 5).
As shown in Fig. 6, the main crystalline compounds found by XRD in
perature (0 °C) since it was obtained, we noticed the presence of
transparent crystals. These were identified to sodium carbonate after
superposing its infrared spectrum with that of the commercial Na2CO3
used in the corresponding step (see Fig. 7). Thus, we concluded that at
low temperature the excess of sodium carbonate present in the solution
was recrystallized.
The photoluminescence analysis of the solution after sodium car-
and more precisely of rare earth elements (see Fig. 8).
However, the study of the optical properties of the recrystallized
sodium carbonate has detected the presence of a broad emission band at
374 nm after excitation at 240 nm (Fig. 9). At this same wavelength, the
pure sodium carbonate has no emission band. In previous works, the
band recorded around 374 nm corresponds to the 2D (5d) 2F2/5 (4f)
transition of the cerium ion Ce3+ in a carbonated matrix (Chen et al.,
2004; Han et al., 2000; Matijvid and Hsu, 1987).
In addition, a selective excitation at the resonance wavelength of
the europium Eu3+ transition 5D0 – 7F2 (at 466 nm) showed the char-
acteristic emission of trivalent europium, observed at 555 nm and
612 nm and assigned respectively to the transitions 5D1 – 7F2 and 5D0 –
7
F2 (see Fig. 10).
Thus, we came to the conclusion that in the carbonated filtrate and
more precisely in the recrystallized sodium carbonate, rare earth ele-
ments (Ce3+ and Eu3+) are present.
4. Discussion
A homogeneous distribution of REEs in the PG fractions has been
proven by ICP/MS (see Section 3.1). A similar result was obtained in a
previous work (Hammas-Nasri et al., 2016) while studying the rare
earths distribution in a fresh produced Tunisian phosphogypsum. Thus,
the PG storage for a long period in slag heaps had no effect on the
homogenous distribution of rare earths in the PG fractions and this
confirms the conclusion drawn as to the genesis of fine PG particles of
similar composition following the sulfuric attack of phosphate ore
(Hammas-Nasri et al., 2016).
The described method has achieved a total rare earth’s enrichment
of 84% by a simple use of aqueous solutions. It is remarkable that a
large quantity of saline solution was used for the first step of PG

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I. Hammas-Nasri et al. Minerals Engineering 132 (2019) 169–174

Y
Sm
La
Eu
100 Ce
10 Gd
90 Pr
Tb
Nd
80 Dy
8
REE's content (ppm)

70

REE's content (ppm)

60
6
50
40
4
30
20 2
10
0 0
>1 1-0.6 0.6-0.3 0.3-0.1 0.1-0.08 0.08-0.053 >1 1-0.6 0.6-0.3 0.3-0.1 0.1-0.08 0.08-0.053
Particle size (mm) Particle size (mm)
(a) (b)
Ho
Er
Tm
6
Yb
Lu
5
REE's content (ppm)

0
>1 1-0.6 0.6-0.3 0.3-0.1 0.1-0.08 0.08-0.053
Particle size (mm)
(c)
Fig. 3. Rare earths distribution in each fraction of the aged Tunisian PG: (a) Y,La,Ce,Pr,Nd (b) Sm,Eu,Gd,Tb,Dy and (c) Ho,Er,Tm,Yb,Lu.

PG DH: CaSO4.2 H2O

S,HH

RI 6000
HH: CaSO4.0.5 H2O
100 RF
5000
Q S : NaCl
90 Q : SiO2
HH

80
4000
HH

70 S
60
Intensity

3000
Count

HH

50
S S
40 2000
HH
DH,Q
DH

30 S
HH

HHHH

20 1000 Q
HH
DH

S
HH
HH

HH

HH
HH

HH
HH

HH

10 Q
0
0
4000 3000 2000 1000
10 20 30 40 50 60 70 80 90
Wavenumbers (cm-1)
2 (degree)
Fig. 4. Superposition of residues (RI and RF) infrared spectra with that of the
Fig. 5. X-ray diffraction pattern of the RI residue.
raw PG.

Na2CO3 from the carbonated filtrate (at low temperature) with photo-
washing, but it should be mentioned that a previous study has already
luminescence technique (Section 3.4). The latter showed the presence
treated the valorization of this washing solution to calcium carbonate
of Ce3+ and Eu3+ characteristic emissions. In order to explain the
and sodium hydrogenosulphate (Hammas et al., 2013a). Residues
phenomenon taking place, we have relied on the results of studies
analysis with different techniques (Sections 3.2 and 3.3) have con-
dealing with the complexation of rare earth elements by carbonate ions
firmed the elimination of impurities from phosphogypsum and ob-
in seawater (Cantrell and Byrne, 1986; Ciavatta et al., 1981; Ferri and
taining a quartz-calcite-sodium carbonate sulfate’s mixture rich in
Salvatore, 1983; Lundqvist, 1982; Ruzaikina et al., 1978). According to
REEs. Rare earths extraction from this solid is under study.
Cantrell and Byrne (Cantrell and Byrne, 1986), carbonate complexes
Another result was found while examining the recrystallized

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I. Hammas-Nasri et al. Minerals Engineering 132 (2019) 169–174

Q : Quartz 2.0
4000
C : Calcite exc = 220 nm
Q
3500 Q B : Sodium Carbonate Sulfate
1.5
3000

2500
1.0

Intensity
2000
Count

1500 0.5
1000 BC C
B B Q
C,Q

500 B BB Q Q
CQ QQC C Q Q 0.0
C
0

10 20 30 40 50 60 70 80 90 -0.5
2 (degree) 280 300 320 340 360 380 400
Wavelength (nm)
Fig. 6. X-ray diffraction pattern of the RF residue.
Fig. 8. Emission spectrum at λexc = 220 nm of the filtrate after sodium carbo-
nate recrystallization.
Table 2
Rare earths enrichment in the obtained residues after each step of the con-
centration method (content expressed in ppm). 350 exc
= 240 nm
Element Raw PG Residue (RI) Residue (RF) Total enrichment
(%) 300

Y 80.81 468.29 528.06 84.7 250

La 54.42 311.22 363.80 85.04
Ce 96.73 429.74 503.72 80.8 200
Intensity
Pr 12.71 56.37 87.02 85.39
Nd 59.42 422.96 509.53 88.34 150
Sm 9.63 42.45 51.17 81.18
Eu 2.29 11.85 15.52 85.24 100
Gd 9.55 44.25 53.48 82.14
Tb 1.46 6.48 7.77 81.2 50
Dy 8.94 38.87 46.42 80.74
Ho 1.81 7.96 9.67 81.28 0
Er 5.47 25.17 30.65 82.15
Tm 0.71 3.54 4.31 83.53 260 280 300 320 340 360 380 400 420 440 460
Yb 5.61 28.61 34.92 83.93 Wavelength (nm)
Lu 0.65 3.48 4.27 84.78
Total REEs content 350.21 1901.24 2250.31 84.44 Fig. 9. Emission spectrum of the recrystallized sodium carbonate at
λexc = 240 nm showing Ce3+ existence.

crushed crystals
Na2CO3 (commercial) These studies have shown that the medium pH is an important
1,0 variable for the complexation phenomenon. Olivier (Pourret, 2006) has
shown that rare earth elements are found in natural waters either as
free species (Ln3+), complexed with sulfate (LnSO4+) at acidic pH, or
0,8 complexed with carbonate (LnCO+ and Ln (CO3)2−) at an alkaline pH.
Thus, carbonate complexes (Ln(CO3)2−) are the predominant species at
alkaline pH (> 8) (Pourret et al., 2007).
Intensity (u.a)

0,6 In the present work, the major species present in the carbonated
solution are Na+ and CO32− ions with a pH of 10.8. The complexation
of europium and cerium was carried out with carbonate ions of the
0,4 solution and cooling at low temperature leads to the recrystallization of
sodium carbonate with incorporation of Eu3+ and Ce3+ ions into its
matrix. Thus, the presence of these ions in the carbonated solution
0,2
suggests the existence of a quantity of rare earths which are linked to
the phosphogypsum matrix by weak bonds, so that after contact with
the carbonated solution, these rare earth elements formed stable com-
0,0
plexes and after cooling they remained preferentially in the re-
4000 3500 3000 2500 2000 1500 1000 500
Wavenumbers (cm )
-1 crystallized Na2CO3 structure.
In order to understand the rare earths location in phosphogypsum, a
Fig. 7. Superposition of the infrared spectrum of crystals formed in the car- recent investigation (Shivaramaiah et al., 2016) showed that, due to the
bonated solution with that of commercial Na2CO3.
rapid phosphogypsum precipitation in the industrial process, europium
(taken as example of rare earth elements) could be present in the form
are the dominant species of rare earth elements in seawater despite the of surface-adsorbed metastable auxiliary phases in the calcium sulfate
presence of various anions such as sulfate, chloride, hydroxide and crystal. With such phase, the europium is associated with phosphate
fluoride. The average constants stability of these complexes are re- and sulfate as counterbalancing ions. In addition, according to Wala-
spectively 2.57 ± 0.13105 and 7.07 ± 0.18105 for Ce3+ and Eu3+. walkar (Walawalkar, 2016; Walawalkar et al., 2016), despite the fact

173
I. Hammas-Nasri et al.
em
= 612 nm
500
466 nm
400
Intensity
Intensity
300
200
400 450 500 550 600
Wavelength (nm)
Fig. 10. (a) Excitation spectrum at λem = 612 nm and (b) Emission spectrum at λexc = 466 nm of the recrystallized Na2CO3 showing Eu3+ existence.
that phosphogypsum’s characterization by XPS and TOF-SIMS denied
the presence of rare earth elements on the surface (Walawalkar et al.,
2016), leaching with deionized water at 80 °C allowed to leach 6% of
REEs.
In all cases, the results obtained during this investigation showed
that rare earths are not all present in the phosphogypsum in the same
way. Their monitoring by different techniques (ICP/MS and PL) proved
the presence of at least two types of bonds between these elements and
PG: A strong binding (for rare earths remaining in the final residue) and
a weak binding (for rare earths migrating with the carbonated filtrate).
Such observations are encouraging in terms of developing a procedure
allowing the exploitation of rare earths presence in the filtrate by their
recovery.
5. Conclusions
The present investigation was interested in treating the phospho-
gypsum consecutively with solutions of NaCl and Na2CO3 in order to
concentrate the rare earths in the final residue thus facilitating their
extraction in an upcoming process. Simple washing the PG with a 25 g/
L saline solution made it possible to reach a rare earths enrichment of
approximately 81%. In addition, treatment with a solution of Na2CO3
(60 g/L) increased this rate to be 84%.
Photoluminescence technique showed the presence of cerium and
europium ions in the recrystallized sodium carbonate at low tempera-
ture. Such result allowed the conclusion according to which at least two
types of bonds between rare earth elements and PG are present: A
strong binding (for rare earths remaining in the final residue) and a
weak binding (for rare earths migrating with the carbonated filtrate).
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