Water Air Soil Pollut (2019) 230:308
https://doi.org/10.1007/s11270-019-4362-z
Adsorption of Rare Earth Elements
onto the Phosphogypsum a Waste Byproduct
M. S. Hagag & A. M. A. Morsy & A. H. Ali &
A. S. El-Shiekh
Received: 8 September 2019 / Accepted: 5 December 2019
# Springer Nature Switzerland AG 2019
Abstract Phosphogypsum (PG), the waste byproduct
resulting from wet process phosphoric acid production,
is employed as a selective and effective adsorbent for
total rare earth elements (REEs) from aqueous solution
and leach liquor. The elaboration of PG adsorbent
complemented after some physical treatments. Adsorp-
tion and elution studies carried out in experimental
batches, including the effect of pH, adsorbent dose,
initial REE concentration, and equilibrium time. Ad-
sorption of REEs onto PG fitted well with Langmuir
isotherm with a theoretical capacity surpassed 357 mg/
g. REEs were effectively eluted from loaded PG with
2 mol L−1 HCl acid with an efficiency of 94%. PG
showed an outstanding selectivity towards REEs in the
presence of many cations and anions, for instance (Fe3+,
UO22+, Ca2+, SO42−, NO3−). Different qualitative tech-
niques such as EDS, SEM, and FTIR used to emphasize
the adsorption of REEs onto PG. The film diffusion
model was the preponderant adsorption mechanism for
REEs; also, the adsorption process has a good accor-
dance with pseudo-second-order kinetic model.
Keywords Phosphogypsum PG . Rare earth elements .
Adsorption . Phosphate Abu-tartour leach liquor and
stripping
M. S. Hagag (*) : A. M. A. Morsy : A. H. Ali :
A. S. El-Shiekh
Nuclear Materials Authority, P.O. Box 530, Maadi, Cairo, Egypt
e-mail: mohammedsobbhy@yahoo.com
1 Introduction
Phosphogypsum PG, a byproduct of wet process
phospophoric acid PA production, has a continual inter-
est for the scientists, including pollution controlling,
recovery and production of many strategic compounds
(Ma et al. 2012). A total of 300 MT is the annual
production of PG (Pacheco-Torgal, F et al. 2012); it
was expected to become a crucial problematic of envi-
ronment in the recent days, due to the intension of PA
production (the essential for many strategic industries,
for instance, the fertilizer production) (Speight 2017).
Production of 1 ton of PA via wet process is followed by
5 tons of PG (Pacheco-Torgal et al. 2018), the huge yield
of PG acts as an environmental and economical burden,
it occupied a wide area from the scientific solicitude.
Many valuable chemical products such as ammonium
sulfate (Kandila et al. 2017) and separation of lantha-
nides (Cánovas et al. 2019; Rychkov et al. 2018) were
the accomplished target for the scientific exploitations of
PG. Many utilities of PG rather than chemical methods
can be summarized: cement production (as an alterna-
tive to gypsum) (Barnes and Bensted 2001, Islam et al.
2017; Manjit 2007), road base, agricultural soil amend-
ment (Hunter 1989; Hentati et al. 2015), in the ceramics
industry (Zhou et al. 2019), and the landfill (Szpadt and
Augustyn 1991). The quantities of REEs in phosphate
ores (the precursors of PG) differ accordingly to the
origin of ores. About 80–85% of the contained REEs
of the phosphate ores co-precipitated in PG during the
production of PA. Even though the word phosphogyp-
sum consists of two words (phospho and gypsum), the
 308 Page 2 of 14 Water Air Soil Pollut (2019) 230:308

phosphorous ratio in PG may be in the range of 1.05– 2 Experimental

7.5% according to the precursor phosphate ores, where-
as the gypsum ratio is 72%. The other chemical constit- 2.1 Chemicals and Solutions
uents of PG for instance, silica, aluminum sulfate, ferric
sulfate, and L.O.I. (free water + adsorbed water + crystal All used chemicals were in analytical grade unless
water). Adsorption at a solid-liquid interface can be oppositely stated. The mineral acids were purchased
defined as the transfer of adsorbate (aqueous phase) to from Adwic. Sodium hydroxide, Arsenazo III, and
active sites of the adsorbent (solid phase), via Van Deer ascorbic acid were purchased from Sigma-Aldrich.
Waals force or chemical bond at the boundary interfaces. The total rare earth elements (REEs) were supplied
Many materials, for instance waste or byproducts after from Nuclear Materials Authority (NMA) projects of
chemical or physical modifications, achieved some separation and refining. Table 1 shows the chemical
merits in selectivity and loading capacity; furthermore, analysis of REEs by ICP-MS. The phosphogypsum
it could be used as promising adsorbents for removing PG, waste materials obtained after production of
many heavy metals from aqueous or waste solutions phosphoric acid, for this work is provided by Abu-
(Youssef et al. 2018). Lanthanides, the elements of Zaable Company, Egypt. The working chemical so-
4F group, showed the similarity or may be identical lutions are prepared by mixing a certain amount of
in its chemical and physical behavior (Forsyth and substance with double distilled water (DDW) or
Hinton 2014). Scandium and Yttrium belong to deionized water (DW) to the required concentration.
REEs, exhibited the same chemical properties, as
well as exist in many ores or REEs resources, it did 2.2 Preparation of REE Solutions
not belong to 4F group so having different physical
and magnetic properties. The REEs have many uses A certain weight of the supplied REE hydroxide 15 g
in life, for instance, ceramics (Yu et al. 2019), was dissolved in conc. HCl acid (50 mL) in water bath at
semiconductors (Yaoguang et al. 2015), glassmak- 85 °C until complete dissolution. The concentration of
ing (Tanabe 2015), solar cell (Znajdek et al. 2018), REE solutions is determined by ICP-MS and UV-VIS
and permanent magnets (Coey 2019). Many re- spectrophotomer and diluted to prepare the required
sources for REEs were monazite, lanthanite, stock standard solution of 4000 mg L−1. Different
xenotime, bastnäsite, allanite, loparite, and phos-
phate rocks (Goodenough et al. 2018). Many chem-
Table 1 ICP-M analysis of the NMA REE standard solution
ical methods are continuously developed and used
for the separation of REEs. The chemical methods REE elements Concentration mg/L
of separation depend on the concentration of REEs.
At the upward trend of REE concentrations, the La 182,625
precipitation as hydroxide or as oxalate is the fa- Ce 222,109.6
vorite (Qi 2018). Besides, the solvent extraction is Pr 67,414.4
also used (Hiskey and Copp 2018). At the down- Nd 55,430.6
ward trend of REE concentrations, the ion ex- Sm 7285.2
change resin (Ang et al. 2017), emulsion membrane Eu 327.8
(Chen et al. 2018), synthetic composite (Xu et al. Gd 2267.4
2018), and bio-adsorption (Gupta et al. 2019) are Tb 497.6
strongly recommended. In this work, REEs have Dy 1119
been extended from acidic leaching of monazite Ho 26
with sulfuric acid. PG is exposed to some physical Er 172.8
treatments and used for REEs removing. The ad- Tm –
sorption of REEs on PG is being innovated with Yb 48.6
dual significant aspects; the first is economical (the Lu 3.6
using of a cheap material as an adsorbent) and the Sc 11.2
second is environmental target (exploitation of a Y 2783.4
waste byproduct).
Water Air Soil Pollut (2019) 230:308 Page 3 of 14 308

concentrations from REEs are prepared via dilution of
the stock standard solution for all batch adsorption
experiments.
2.3 Preparation of Phosphogypsum PG as Adsorbent
experiments complemented, the solid phase was sepa-
rated from the aqueous phase with Whatman filter paper
42 and REE concentration was determined spectropho-
tometrically in the aqueous phase.

One hundred grams of PG was washed several times 3 Results and Discussion
with DDW for removing unstable substances, ashes,
and wastes; subsequently, it will be filtered continuously 3.1 Characterizations of PG Adsorbent
until pH of filtrate solution increase to 7. After filtration,
PG is dried at 80 °C for 12 h and ignited at 200 °C for 3.1.1 FTIR Secptrum of PG Before and After REE
3 h. Table 2 shows the chemical constituents of PG Adsorption
related to the study.
Figure 1 shows FTIR spectrum of PG before and after
2.4 RRE Spectrophotometric Determination REE adsorption. There are some changes in either mag-
nitude of the bands or intensity before and after adsorp-
The concentration of REE solutions was spectrophoto- tion (Karge et al. 2004), which may give some indica-
metrically determined at 650 nm, through the addition tions about the adsorption of REEs onto PG. Bands at
of 4 mL of 0.05% arsenazo III, 2 mL of 1% L-ascorbic 1124.43 cm−1 changed to 1056 cm−1, also bands at
acid, and 1 mL of formate buffer and pH is adjusted to 733.7 cm −1 disappeared, and bands at 600 cm −1
2.6. UV-VIS Shimadzu 1401 spectrophotometer was changed to 540 cm−1. The difference in the value of
used in all spectrophotometric measurements. The con- absorption peaks of PG and the PG loading with REEs
centration of REEs must not exceed over 1.5 mg L−1 (and in some cases in peak intensity) acts as an evidence
(Marczenko 1976). for occurring adsorption of REEs onto PG. The spec-
trum of PG manifested the presence of various absorp-
2.5 Adsorption and Elution Experiments tion bands assigned fundamentally to the inorganic sul-
fur compounds, strong, intense bands at 1124.5 cm−1
represented stretch vibration of the S–O bond (El Afifi
All adsorption and elution experiments carried out in
batch mode. Fifty-milliliter polypropylene tubes were et al. 2009; El-Didamony et al. 2013). There are SO4 υ4
vibrational bands (Nosov et al. 1976) near 600–
used in all experiments. About 25 mL of REE standard
680 cm−1. Bands at 3447.5 cm−1 and 1641.9 cm−1 rep-
solution and 100 mg of PG adsorbent were used usually
in all adsorption experiments unless otherwise stated resented OH vibrations as moisture in PG (El-
Didamony et al. 2013).
and the temperature kept constant at 22 ± 1 °C (ambient
temperature) unless otherwise stated. The checker GFL
(made in England) is used for all adsorption and elution 3.1.2 SEM Analysis
experiments. After the adsorption and elution
The SEM images of PG before and after REE adsorp-
Table 2 Main constituents of Abu-Zaable company tion. Figure 2 a illustrates the SEM image of the PG
phosphogypsum surface before REE adsorption; it showed a texture with
a low porous and homogenous surface where CaSO4
Components Percentage %
phase was predominant. Figure 2 b displays the SEM of
CaSO4 67% L.I.O. 25% PG surface after REE adsorption. There are particles of
SiO2 1.9% Total REE 441 mg/g various dimensions and shapes also; the image exhibits
P2O5 4% U 6 mg/g a presence of well-defined crystalline structure and
Fe2O3 1.8% Th 15 mg/g some of the amorphous matters. The particles character-
Na2O 0.2% ized by variable size, dimensions, and pore shapes; there
K2O 0.21% are aggregations of different particles having the size (5,
TiO2 0.6% 10, 20, 50, and 100 μm) extensively present. Differ-
ences between SEM images in Fig. 2 a and b clarified
 308 Page 4 of 14 Water Air Soil Pollut (2019) 230:308

PG after REEs adsorption

50 a PG before adssorption
45

40

35
3459 1655
600
30 1121

b
25
B

20

15

10 1644

540
5

0 3447 1056

4000 3500 3000 2500 2000 1500 1000 500

-1
cm
Fig. 1 FTIR spectra of PG before REE adsorption (a) and after (b)

that all cavities and gaps present in PG surfaces before
REE adsorption are completely occupied with the
adsorbed REEs.
3.1.3 EDS Analysis
EDS chart gives a descriptive view of some chemi-
cal elements present in the PG before and after REE
adsorption. EDS displays a qualitative analysis rath-
er than a quantitative analysis. Figure 3 a represents
the EDS chart for PG before adsorption. The ele-
ments Ca, Al, S, Fe, and Si are present; they were
from the major chemical constituent of PG. Also,
Fig. 3b shows the EDS chart for PG after adsorp-
tion; it was noticable that all the previous elements
that present before adsorption are present as well as
some REEs such as La, Ce, Nd, Sm, Pr, Gd; this
may give evidence for the adsorption of REEs onto
PG adsorbent. The characteristic signals of Y and
Dy are not shown in EDS chart; this may be attrib-
uted to EDS spectrometers when used for specimens
with complex topography introduce uncontrolled
geometric factors which modify X-ray generation
and propagation, resulting in tremendous errors
(Newbury and Ritchie 2013). EDS signals are usu-
ally obtained from the upper few micrometers of the

Fig. 2 SEM images of PG surfaces before REE adsorption (a) and after (b)
Water Air Soil Pollut (2019) 230:308 Page 5 of 14 308

Fig. 3 EDS charts for PG before REE adsorption (a) and after adsorption (b)

sample (the electrons in the beam penetrate few
microns into the surface), i.e., it is not a bulk anal-
ysis technique (Ul-Hamid 2018).
4 Adsorption Measurements
4.1 Impact of pH on Adsorption Efficiency and REE
Uptake
The effect of pH acts as the prevailing factor in the
adsorption efficiency and the loading capacity of
solid/liquid extraction system; it determines the per-
formance, workability, and pH range for the adsor-
bents. Whenever pH range of adsorbent is wide, it
increases the potentiality of adsorption from many
waste solutions or leach liquors. Many cations pre-
cipitated from waste solutions at pH > 3, for instance
the precipitation of iron starts at pH 3.5. The effect
of pH on REE adsorption and the loading capacity
of PG was investigated. The pH ranges 1–5) ± 0.1
are set, whereas the other experimental conditions
are constant (1000 mg L−1 REE concentration, 1 h
equilibrium time, and 100 mg/25 mL dose ratio).
Figure 4 illustrates that at pH < 2 ± 0.1 it was a
noteworthy decreasing in REE adsorption efficiency
and uptake to 44% and 110 mg g−1, respectively;
this may be attributed to the competition with

Fig. 4 Effect of pH on adsorption Adsorption %

efficiency and uptake of REEs on REEs Uptake
300
PG adsorbent
100
250

75 200
Adsorption %

REEs Uptake

150
50

100

25
50

0 0
1 2 3 4

pH
 308 Page 6 of 14 Water Air Soil Pollut (2019) 230:308

hydrogen ions (it is recognized as the smallest ion PG surface with REE ions and any augmentation in con-
and has the highest mobility) with REEs (Ramasamy centration never reflected in the increase of PG adsorption
et al. 2019); furthermore, at this low pH, an electro- capacity.
static repulsion is planted between PG surface and
the REE ions which may be attributed to that PG
4.3 Impact of Equilibrium Time on Adsorption
surface was positively charged due to the tremen-
Efficiency and Uptake
dous presence of proton (Zhao et al. 2016). At pH >
2 ± 0.1,adsorption efficiency reaches 99% and up-
The equilibrium time has a crucial impact in the adsorp-
take 248.1 mg g−1 for REEs; therefore, pH 3 ± 0.1 is
tion process, the adsorption efficiency and uptake of
considered as the optimum. At pH > 3.5 ± 0.1, the
REEs on PG is examined at different time intervals 5–
precipitation of Ce4+ took place (Bouchaud et al.
60 min and the other conditions were pH 3 ± 0.1, initial
2012); furthermore, REEs are precipitated as hy-
concentration 2000 mg L−1, and dose ratio 200 mg/
droxides at pH (6–11).
25 mL at ambient temperature. Figure 6 illustrates that
adsorption efficiency and uptakes of REEs on PG sur-
face grew to 43% and 109 mg g−1, respectively, after
4.2 Impact of Initial Total REE Concentration
5 min, whereas prolonged equilibrium time to 45 min
on Adsorption Efficiency and Uptake
was sufficient for achieving adsorption efficiency of
99% and uptakes of 248 mg g−1. When the equilibrium
In order to study the effect of REE initial concentrations on
time surpasses over 45 min, the increasing in uptake was
adsorption efficiency and loading capacity, different concen-
inconsiderable. The optimum equilibrium time for REE
trations of REEs ranging from 500 to 5000 mg L−1 were set,
adsorption was 45 min.
the other conditions were pH 3 ± 0.1, equilibrium time 1 h,
and dose ratio 200 mg/25 mL at ambient temperature. Initial
REE concentration has a clear influence for adsorption 4.4 Impact of Adsorbent Dose on Adsorption Efficiency
efficiency and uptake on PG. Figure 5 shows that by and Uptake
increasing initial REE concentration, adsorption efficiency
decreased whereas, the uptake increased to 350 mg g−1, The effect of PG weight on adsorption efficiency and
until concentration of (3000-5000) mg L−1. But at concen- uptake of REEs on PG surface was studied via variation
trations less than 3000 mg L−1, an emphatic increasing in of PG weights in the range 25, 50, 75, 200 mg/25 mL.
adsorption efficiency is formed, while the uptake is de- The other experimental conditions were pH 3 ± 0.1,
creased, this attributed to saturation of active sites on the initial concentration of 1200 mg L−1, and equilibrium

Fig. 5 Effect of initial REE Adsorption %

concentration on adsorption % REEs Uptake
400
and uptake on PG
100 350

300

75 250
Adsorption %

REEs Uptake

200

150
50

100

50
25
0
0 1000 2000 3000 4000 5000

REEs Concentration mg/L

Water Air Soil Pollut (2019) 230:308 Page 7 of 14 308

Fig. 6 Effect of equilibrium time Adsorption %

of REE adsorption and uptake on REEs Uptake
350
PG
100
300

250
75

Adsorption %

REEs Uptake
200

50
150

100
25

50

0 0
0 10 20 30 40 50 60

Time

time 85 min. Figure 7 shows that with increasing adsor-
bent dose, the adsorption efficiency is augmented; it is
due to the increasing amount of adsorbent; moreover,
reinforcing the chance of conducting adsorbents particle
with RREs ions, also increasing the concentration of
active site on PG surface. The REE uptake has the
optimum value of 352 mg g−1 at adsorbent dose of
25 mg/25 mL; furthermore, at adsorbent doses ranging
from 25 to 50 mg/25 mL, REE uptake was mostly being
constant. Increasing of adsorbent doses (above 50 mg/
25 mL) has a negative effect on the loading capacity, due
to 50 mg of PG was enough to adsorb all REEs at the
concentration (1200 mg L−1). In any additional PG
weights over 50 mg, there are no any REEs present in
the feeding solution for adsorption.
4.5 Impact of Interfering Ions on Adsorption Efficiency
and Uptake
Different anions and cations such as nitrate, sulfate, chlo-
ride, sodium, calcium, nickel, uranium, thorium, and iron
(in a concentration of 1200 mg L−1) were used to inves-
tigate its effect on REE adsorption efficiency. The other
experimental conditions were pH 3 ± 0.1, initial REE

Fig. 7 Effect of adsorbent dose Adsorption %

ratio on adsorption and uptake of REEs Uptake
400
REE on PG
100
350

300
75
Adsorption %

REEs Uptake

250

50 200

150

25
100
20 40 60 80 100 120 140 160 180 200 220

PG Weight
 308 Page 8 of 14 Water Air Soil Pollut (2019) 230:308

Table 3 Impact of interfering ion adsorption onto efficiency and used for the aqueous solid extraction. The most common
uptake of total REE on PG as an adsorbent
models used in adsorption isotherm were Langmuir and
Interfering Uptake of REE in Uptake of REE in % of REE Freundlich model (Azizian et al. 2018; Singh et al. 2018).
ions absence of absence of uptake
interfering ions interfering ions reduction
mg/g mg/g
4.7 Langmuir Isotherm
Sodium 300 293.7 2.1
Calcium 300 295.5 1.5 Adsorption of a homogeneous monolayer of adsorptive
Nickel 300 292 2.8 ions on the confined number of identical active sites of
Uranium 300 285 4 adsorbent surface was the main postulate of the Langmuir
Thorium 300 291.6 2.9 model. The Langmuir model is represented by the follow-
Iron 300 265 12.4 ing equation (Youssef et al. 2018; Youssef et al. 2019).
Nitrate 300 300 0
Sulfate 300 300 0
Chloride 300 295 1.6
Ce =qe ¼ 1=bQo þ Ce =Qo ð1Þ

concentration 1200 mg L−1, 100 mg/25 mL dose ratio,

and equilibrium time 1.25 h. Table 3 declares that the
presence of any considerable interfering ions under study
did not affect on the adsorption efficiency of REEs except
iron ions. At 1200 mg L−1 of iron REEs, uptake de-
creased about 12.4% (uptake reduced from 300 to
265 mg/g). It is clear that the interfering effects of iron
are higher than thorium. In the adsorption process of
heavy metals or at potentiometric sensors, iron has im-
portant interfering effects with respect to many cations
with higher or lower oxidation states. Even though the
platinum group elements (Ru, Rh, Pd, Os, Ir, and Pt)
having oxidation states > 3 + {Ru+4, Rh+4, Pd+4, Os+6,
Ir+4, and Pt+4}, the adsorption of REEs was not affected
by the presence of platinum group elements (Mosai et al.
2019). Besides, the adsorption of tri-valent REEs is de-
creased in the presence of di-valent cations Fe2+ and
Zn2+, Mn2+ at adsorbents the recycled tire carbon black
(RTCB) and TiO2 nanotubes, respectively (Jebali et al.
2019; Smith et al. 2016).
where Ce is the concentration of REE ions at equilibrium
(mg L−1), qe is the adsorbed REEs per unit mass of
adsorbent at equilibrium (mg g−1). Qo(mg g−1) is the
maximum amount of REEs per unit mass of PG for
developing a saturated homogeneous monolayer on the
PG surface and b(mg L−1)is a constant related to the
affinity of the binding sites. Plotting of Ce/Qoversus Ce
resulted a straight line exhibiting a slope of (1/Qo) and
an intercept of 1/bQo. Figure 8 shows that the theoretical
loading capacity of PG was 357 mg g−1 which is con-
cordant with the practical loading capacity
(350 mg g−1), consequently the adsorption of REEs on
PG convenient with the Langmuir adsorption model.
Table 4 illustrates the Langmuir constants and
specifications.
10
8

4.6 Adsorption Isotherms

e
Ce/q

Adsorption isotherm is a graphical relation of adsorption

2
process between the amount of adsorbed molecules on
adsorbent surfaces relative to the adsorbate equilibrium 0
concentration at bulk. The design of adsorption process
of REEs on PG surface is optimized for setting the most 0 500 1000 1500 2000 2500 3000 3500 4000

adequate correlation for the equilibrium curves at con- Ce

stant temperature. Adsorption isotherms applied com- Fig. 8 Langmuir adsorption isotherm model for adsorption of
monly for gas-solid adsorption, but it was extensively REEs onto PG
Water Air Soil Pollut (2019) 230:308 Page 9 of 14 308

Table 4 Langmuir and Freundlich isotherm model specifications 4.9 Adsorption Mechanism
for Rees adsorption on PG

Langmuir isotherm model Freundlich isotherm model
qmax b R2 n Kf R2
357.14 0.0121 0.995 4.46 61.1 0.877
4.8 Freundlich Isotherm
Freundlich isotherm is generally applied or valid for the
heterogeneous surfaces; it postulates that adsorption of
ions in surface occurs in multilayer sorption. Freundlich
model is represented by the following empirical equa-
tion (Gupta et al., 2019; Vijayakumar et al. 2009):
qe ¼ K F Ce 1=n
where KF and n are the Freundlich constants which
depend on the nature of the adsorbent and the adsorbate.
Figure 9 represents a graph for correlating of lnqe
against lnCe. Table 4 shows that, at the adsorption of
REEs on PG surface, the R2 value of the Langmuir
isotherms is 0.995 much close to 1, whereas R2 obtained
by the Freundlich isotherms is 0.877. Hence, the adsorp-
tion characteristics of REEs on PG were compatible
with the Langmuir isotherm model rather than
Freundlich isotherms. Consequently, the adsorption of
REEs on PG surface was only a homogenous adsorption
via formation of monolayer of REEs at the homogenous
PG surface.
The description of the adsorption mechanism for REEs
onto PG could occur via the intraparticle diffusion mod-
el and the liquid film diffusion model; these explain the
mechanism in steps: (i) movement of REEs from the
bulk of the solution to the PG surface (bulk diffusion),
(ii) REEs diffuse to PG surface from the boundary layer
(film diffusion), (iii) REE transportation from PG sur-
face to the inner pores of the particle (intraparticle
diffusion or pore diffusion), (iv) active sites on PG
adsorped REEs (via ion exchange or chelation)
(Ahmad and Kumar 2011; Crini et al. 2007; Gupta and
Bhattacharyya 2011).
4.10 The Intraparticle Diffusion Model
Weber and Morris predict mathematical equations for
the intraparticle diffusion model which may express in
the form: qt = kit1/2 + C where qt is the amount of
adsorbed REEs per unit mass of PG (uptake) at time t.
k i is the intraparticle diffusion rate constant
(mg g−1 min−1/2), t is the time (min), and C is the
intercept (mg g−1); it donates the conception on the
thickness of the boundary layer. We plot qt against t1/2.
If the REE adsorption onto PG fits with the intraparticle
diffusion model as a controlling step, it produces a linear
relationship and the line passes to the origin (Ahmad
and Kumar 2011; Hagag 2019). Figure 10 shows that
the straight line did not pass through the origin; this
implies that the intraparticle diffusion model was not the
250

10

200
8

150
6
qt
lnqe

100
4

50
2

0 0
2 3 4 5 6 7 8 9 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
lnCe 1/2
t
Fig. 9 Frendulish adsorption isotherm model for adsorption of Fig. 10 The intraparticle diffusion model for REE adsorption onto
REEs onto PG PG
 308 Page 10 of 14 Water Air Soil Pollut (2019) 230:308

Fig. 11 The liquid film diffusion Time (min)

model for REE adsorption onto 0
PG 0 5 10 15 20 25 30 35

-0.5

ln(1-F) -1

-1.5

-2

-2.5

only controlling step; furthermore, this was a signifi-
cance of some degree of boundary layer control. It is
clear that the rate of adsorption not controlled only with
the intraparticle diffusion model, but there are other
process done.
4.11 The Liquid Film Diffusion Model
The liquid film diffusion model mathematically
expressed in the equation ln (1-F) = -Kf t, where F was
the fractional attainment of the equilibrium F = qt/qe. Kf
was the diffusion rate parameter in the film diffusion
model and t was the time per minute. We plot t against ln
(1-F). Figure 11 shows the straight line relationship for t
and ln(1-F) passed through the origin. Otherwise, the
intraparticle diffusion model, the liquid film diffusion
model, was the controlling step (Crini etal., 2007; Gupta
and Bhattacharyya 2011; Siyal et al. 2018).
4.12 Chemical Kinetics
adsorbent at time t (mg g−1), and ks1 is the pseudo-first-
order rate constant (min−1). This equation describes the
sorption of the liquid/solid (REEs/PG) system and ex-
tensively characterizes the sorption kinetics. Plotting of
ln(qe − qt) versus time gives the value of K1 from inter-
cept and slope. Figure 12 shows a linear relationship
between t and ln(qe − qt), if a straight line produced the
adsorption may exhibit a pseudo-first order kinetic be-
havior (Li et al. 2019).
4.14 Pseudo-Second-Order Kinetic Model
The pseudo-second-order kinetic model obtained
from the equation t/qt = 1/k2qe2 + 1/qt + t where
K2 the rate constant of the pseudo-second-order.
The plotting of t/qt versus t, K2 is calculated from
the intercept (Gupta et al. 2019). If the adsorption
process fitted with the pseudo-second-order kinetic
5.0

Determination of the rate of the chemical reaction can 4.8

proceed through studying the chemical kinetics. It also 4.6

gives a vision for the mechanisms of chemical processes
4.4
across studies the speed of sorption with interval time.
ln(qe-qt)

There are different kinetics model that describes the 4.2

mechanisms of adsorption process: pseudo-first-order 4.0
kinetic model and pseudo-second-order kinetic model.
3.8

4.13 Pseudo-First-Order Kinetic Model 3.6

3.4
Lagergren derived pseudo-first-order kinetic model 5 10 15 20 25 30
equation ln (qe − qt) = lnqe − ks1t where qe is the amount Time (min)
of REEs adsorbed onto PG at equilibrium (mg g−1), qt is Fig. 12 Pseudo-first-order kinetics model for REE adsorption
the amount of REEs adsorbed on the surface of the PG onto PG
Water Air Soil Pollut (2019) 230:308 Page 11 of 14 308

0.15 80

70

60
0.10
50

Elution %
t/qt

40

0.05 30

20

10

0.00
0
5 10 15 20 25 30
Hydrochloric Acid Nitric Acid Sulfuric Acid
Time (min)
Fig. 14 Effect of eluting agent type on desorption efficiency of
Fig. 13 Pseudo-second-order kinetic model for REE adsorption REEs from the loading PG
onto PG

1000 mg L−1, 100 mg/25 mL dose ratio, and equilibrium

model, the rate-limiting step may be chemical ad-
sorption with a valency forces via the exchange of
electrons between the adsorbent and the metal ions
(Idris et al. 2013). Figure 13 shows the graph
relation between t/qt versus t for the adsorption
of REEs onto PG. Table 5 summarizes all con-
stants and parameters of the pseudo-first-order ki-
netic model and pseudo-second-order kinetic mod-
el. Table 5 shows that the value of R2 in the
pseudo-second-order kinetic model is 0.9929 that
is closer to 1, but the value of R2 in the case of
pseudo-first-order kinetic model is 0.9817. Besides
the value of qe in the pseudo-second-order kinetic
model is 270 mg g−1 which is closer to the prac-
tically detected 250 mg g−1, whereas the value of
qe in pseudo-first-order kinetic model is
188 mg g−1. It was clear that adsorption of REEs
onto PG controlled with the pseudo-second-order
kinetic model.
time 30 min).
4.16 Effect of Eluting Agent Type
Different eluting agents (HCl, HNO3, and H2SO4) used
with concentration 1.5 N. The other eluting conditions
were 30 min equilibrium time, 100 mg/25 mL dose ratio).
HCl gave the optimum elution efficiency of 80%.
Figure 14 illustrates the different elution efficiency of
various mineral acids for REEs eluting from loaded PG.
4.17 Effect of Eluting Agent Concentration
Different concentrations of HCl acid ranging from 0.5 to
2.5 N were used while the other elution conditions were
30 min equilibrium time, 100 mg/25 mL dose ratio. The
results are illustrated on Fig. 15; it is clear that the
100

4.15 Elution Experiments 90

80
All optimum conditions that resulted from adsorption
Elution %

experiments were applied (pH 3, initial concentration 70

60
Table 5 Pseudo-first-order kinetic model and pseudo-second-or-
der kinetic model constants and specifications 50

Pseudo-second-order kinetic Pseudo-first-order kinetic 40

model model
30
R2 K1 qe R2 K2 qe 0.5 1.0 1.5 2.0 2.5
Hydrochloric Acid Concentration mol/L

0.9929 0.0571 270 mg/g 0.9817 0.0339 188 mg/g Fig. 15 Effect of HCl concentration on desorption efficiency of
REE from the loading PG
 308 Page 12 of 14
100
75
Elution %
50
25
0 352 mg g−1. Also, the loaded PG desorbed REEs with
5 10 15 20 25 30
Time (min)
Fig. 16 Effect of equilibrium time on desorption efficiency of
REE from the loading PG
highest elution efficiency reached 94% obtained at 2 N
HCl. At HCl concentrations > 2 N, there is no any
change in elution efficiency of REEs from loaded PG.
4.18 Effect of Equilibrium Time
The different equilibrium times for REE desorption
from loaded PG varied from 10 to 60 min, while keep-
ing the other elution conditions were 2 N HCl, 100 mg/
25 mL dose ratio. Figure 16 shows that the highest
elution efficiency of REEs reached 94% at 30 min.
4.19 Case Study
The leach liquor of REEs obtained from acidic leaching
of phosphate Abu-Tartour. The optimum leaching con-
ditions were 90 °C, 1 h leaching time, 3:1 liquid/solid
ratio, and 3 M HCl; the concentration of REE in leach
liquor was 2100 mg L−1. The obtained leach liquor
subjected to the previous optimum adsorption conditions
(2000 mg L−1 REE, equilibrium time 45 min, pH 2.5 ±
0.1 to avoid precipitation and the dose ratio 2 g/L). It was
obvious that the adsorption efficiency reached 85%,
while only about 1787 mg L−1 of REEs was adsorbed
onto PG adsorbent. The optimum elution conditions were
2 N HCl, 30 min equilibrium time, and 0.1 g/25 mL dose
ratio); the elution efficiency reached 94%. The obtained
solution contains 1675 mg L−1 of REEs. The pH of
stripping solution was adjusted to pH 1.2 ± 0.1 and REEs
were precipitated as REEs-oxalate with the addition of
12% oxalic acid. The REEs-oxalate was calcinated at
Water Air Soil Pollut (2019) 230:308
250 °C in an electric furnace. Recovery of REEs was
76.1% and purity was 98%.
5 Conclusion
Phosphogypsum (PG) selectively adsorbed REEs from
aqueous chloride solution. The optimum adsorption
conditions were pH > 2.5 ± 0.1, equilibrium time
45 min, and dose ratio of 100 mg/25 mL; it exhibits an
adsorption efficiency of 99% and loading capacity was
2 N HCl and 30 min equilibrium time, including elution
efficiency of 94%. The only considerable interference
was from iron. It causes about a 12.4% reduction in REE
uptake and adsorption efficiency onto PG adsorbent.
Many cations and anions like nitrate, sulfate, chloride,
sodium, calcium, nickel, uranium, and thorium cause
slight or have not any significant effect on the adsorp-
tion of REE onto PG. Phosphate leach liquor solution
(PLLS) (extended from phosphate rock Abu-tatour pla-
teau from the Egyptian western desert) was the case
study. It contains 2103 mg L−1 of REEs and subjected
to all the optimum adsorption and desorption conditions.
PG adsorbed REEs from PLLS with the loading capac-
ity of 1787 mg L−1 accomplishing an adsorption effi-
ciency of 85% and the stripping efficiency reached 94%.
The desorption REE solution is subjected to precipita-
tion with 12% oxalic acid at pH 1.2 and achieving REE
recovery of 76.1% with a purity of 98%.
References
Ahmad, R., & Kumar, R. (2011). Adsorption of Amaranth dye
onto alumina reinforced polystyrene. Clean – Soil, Air, Water,
39(1), 74–82.
Ang, K. L., Li, D., & Nikoloski, A. N. (2017). The effectiveness of
ion exchange resins in separating uranium and thorium from
rare earth elements in acidic aqueous sulfate media. Part 1.
Anionic and cationic resins, Hydrometallurgy, 174, 147–155.
Azizian, S., Eris, S., & Wilson, L. D. (2018). Re-evaluation of the
century-old Langmuir isotherm for modeling adsorption phe-
nomena in solution. Chemical Physics, 513, 99–104.
Barnes, P., & Bensted, J. (2001). Structure and Performance of
Cements (p. 259). Spon Press.
Bouchaud, B., Balmain, J., Bonnet, G., & Pedraza, F. (2012). pH-
distribution of cerium species in aqueous systems. Journal of
Rare Earths, 30(6), 559–562.
Cánovas, C. R., Chapron, S., Arrachart, G., & Pellet-Rostaing, S.
(2019). Leaching of rare earth elements (REEs) and impuri-
ties from phosphogypsum: A preliminary insight for further
Water Air Soil Pollut (2019) 230:308
recovery of critical raw materials. Journal of Cleaner
Production, 219, 225–235.
Chen, Q., Ma, X., Zhang, X., Liu, Y., & Yu, M. (2018). Extraction
of rare earth ions from phosphate leach solution using emul-
sion liquid membrane in concentrated nitric acid medium.
Journal of Rare Earths, 36(11), 1190–1197.
Coey, J. M. D. (2019). 2019, perspective and prospects for rare
earth permanent magnets. Engineering, In press, Available
online. https://doi.org/10.1016/j.eng.2018.11.034.
Crini, G., Peindy, H. N., Gimbert, F., & Robert, C. (2007).
Removal of basic green 4 (malachite green) from aqueous
solutions by adsorption using cyclodextrin-based adsorbent:
Kinetic and equilibrium studies. Separation and Purification
Technology, 53, 97–110.
El Afifi, E. M., Hilal, M. A., Attallah, M. F., & EL-Reefy, S. A.
(2009). Characterization of phosphogypsum wastes associat-
ed with phosphoric acid and fertilizers production. Journal of
Environmental Radioactivity, 100, 407–412.
El-Didamony, H., Gado, H. S., Awwad, N. S., Fawzy, M. M., &
Attallah, M. F. (2013). Treatment of phosphogypsum waste
produced from phosphate ore processing. Journal of
Hazardous Materials, 244-245, 596–602.
Forsyth, M., & Hinton, B. (2014). Rare earth-based corrosion
inhibitors. In T. Behrsing, G. B. Deacon, & P. C. Junk
(Eds.), The chemistry of rare earth metals, compounds, and
corrosion inhibitors (pp. 2–37). Woodhead Publishing
Series- Elsevier Ltd..
Goodenough, K. M., Wall, F., & Merriman, D. (2018). The rare
earth elements: Demand, Global Resources, and Challenges
for Resourcing Future Generations. Natural Resourses
Research, 27, 201.
Gupta, S. S., & Bhattacharyya, K. G. (2011). Kinetics of adsorp-
tion of metal ions on inorganic materials: A review. Advances
in Colloid and Interface Science, 162, 39–58.
Gupta, N. K., Gupta, A., Ramteke, P., Sahoo, H., & Sengupta, A.
(2019). Biosorption-a green method for the preconcentration
of rare earth elements (REEs) from waste solutions: A re-
view. Journal of Molecular Liquids, 274, 148–164.
https://doi.org/10.1016/j.molliq.2018.10.134
Hagag, M.SA., 2019, Comparative study of fabricated composites
based on phosphogypsum and Al-hydroxide for uranium
separation from aqueous and waste solutions, https://doi.
org/10.1080/03067319.2019.1670826.
Hentati, O., Abrantes, N., Caetano, A. L., Bouguerra, S.,
Gonçalves, F., Römbke, J., & Pereiraef, R. (2015).
Phosphogypsum as a soil fertilizer: Ecotoxicity of amended
soil and elutriates to bacteria, invertebrates, algae and plants.
Journal of Hazardous Materials, 294, 80–89.
Hiskey, J. B., & Copp, R. G. (2018). Solvent extraction of yttrium
and rare earth elements from copper pregnant leach solutions
using Primene JM-T. Minerals Engineering, 125, 265–270.
Hunter, A., 1989, Use of Phosphogypsum fortified with other
selected essential elements as a soil amendment on low
Cation exchange soils. Final report, FIPR publication no.
01-034-081.
Idris, S., Alotaibi, K. M., Peshkur, T. A., Anderson, P., Morris, M.,
& Gibson, L. T. (2013). Adsorption kinetics: Effect of adsor-
bent pore size distribution on the rate of Cr(VI) uptake.
Microporous and Mesoporous Materials, 165, 99–105.
Islam, G. M. S., Chowdhury, F. H., Raihan, M. T., Amit, S. K. S.,
& Islam, M. R. (2017). Effect of Phosphogypsum on the
Page 13 of 14 308
properties of Portland cement. Procedia Engineering, 171,
744–751.
Jebali, R., Triki, M., Alomair, N.A., Kochkar, H., 2019, From
adsorption of rare earth elements on TiO2 nanotubes to
preconcentration column application microchemical journal,
149, 104.
Kandila, A. T., Cheira, M. F., Gado, H. S., Soliman, M. H., & Akl,
M. H. (2017). Ammonium sulfate preparation from phospho-
gypsum waste. Journal of Radiation Research and Applied
Sciences, 10(1), 24–33.
Karge, H., Geidel, E., & Weitkamp, J. (2004). Mol. Sieves science
and technology-characterization I. Vibrational Spectroscopy,
72.
Li, L., Lu, W., Ding, D., Dai, Z., Cao, C., Liu, L., & Chen, T.
(2019). Adsorption properties of pyrene-functionalized nano-
Fe3O4 mesoporous materials for uranium. Journal of Solid
State Chemistry, 270, 666–673.
Ma, L., Du, Y., Niu, X., Zheng, S., & Zhang, W. (2012). Thermal
and kinetic analysis of the process of thermochemical de-
composition of Phosphogypsum with CO and additives.
Industrial and Engineering Chemistry Research, 51, 6680–
6685.
Manjit, S. (2007). Treating waste phosphogypsum for cement and
plaster manufacture. Cement and Concrete Research, 32(7),
1033–1038.
Marczenko, Z. (1976). spectrophotometric determination of ele-
ments. Harwood, New York: John Wiley and Sons. 1976
Mosai, A. K., Chimuka, L., Cukrowska, E. M., Kotzé, I. A., &
Tutu, H. (2019). The recovery of rare earth elements (REEs)
from aqueous solutions using natural zeolite and Bentonite.
Water, Air, and Soil Pollution, 230, 188.
Newbury, D. E., & Ritchie, N. W. M. (2013). Is scanning Electron
microscopy/energy dispersive X-ray spectrometry (SEM/
EDS) quantitative? Scanning, 35, 141–168. https://doi.
org/10.1002/sca.21041
Nosov, V. N., Frolova, N. G., & Kamyshov, V. F. (1976). IR
spectra of calcium sulfate semihydrates. Journal of Applied
Spectroscopy, 24, 509.
Pacheco-Torgal, F., Jalali, S., & Fucic, A. (2012). Toxicity of
building materials (p. 221). Woodhead Publishing Limited.
Pacheco-Torgal, F., Shi, C., & Sanchez, A. P. (2018). Carbon
dioxide sequestration in Cementitious construction materials
(p. 199). Elsevier.
Qi, D. (2018). Hydrometallurgy of Rare Earths: Extraction and
Separation (p. 701). Elsevier.
Ramasamy, D. L., Puhakka, V., Doshi, B., Iftekhar, S., &
Sillanpää, M. (2019). Fabrication of carbon nanotubes rein-
forced silica composites with improvedrare earth elements
adsorption performance. Chemical Engineering Journal,
365, 291–304.
Rychkov, V. N., Kirillov, E. V., Kirillov, S. V., Semenishchev, V.
S., Bunkov, G. M., Botalov, M. S., Smyshlyaev, D. V., &
Malyshev, A. S. (2018). Recovery of rare earth elements from
phosphogypsum. Journal of Cleaner Production, 196, 674–
681.
Singh, B. P., Gupta V. K., and Passari, A. K. (2018). New and
Future Developments in Microbial Biotechnology and
Bioengineering Actinobacteria: Diversity and
Biotechnological Applications,Chapter 18- Ashok Bankar
and Geetha Nagaraja1, Elsevier B.V. Recent Trends in
 308 Page 14 of 14
Biosorption of Heavy, Metals by Actinobacteria, Chapter 18,
pp 265.
Siyal, A. A., Shamsuddin, M. R., Khan, M. I., Rabat, N. K.,
Zulfiqar, M., Man, Z., Siame, J., & Azizli, K. A. (2018). A
review on geopolymers as emerging materials for the adsorp-
tion of heavy metals and dyes. Journal of Environmental
Management, 224, 327.
Smith, Y. R., Bhattacharyya, D., Willhard, T., & Mano Misra, M.
(2016). Adsorption of aqueous rare earth elements using
carbon black derived from recycled tires. Chemical
Engineering Journal, 296, 102–111.
Speight, J. G. (2017). Environmental Inorganic Chemistry for
Engineers, Elsevier Inc., pp 149.
Szpadt, R., & Augustyn, Z. (1991). Environmental Pollution in the
Vicinity of a Waste-Gypsum Landfill. In L. Pawlowski, W. J.
Lacy, & J. J. Dlugosz (Eds.), Chemistry for the Protection of
the Environment. Environmental Science Research (Vol. 42,
pp. 387–399). Springer.
Tanabe, S. (2015). Glass and Rare-Earth Elements: A Personal
Perspective. International Journal of Applied Glass Science,
6(4), 305–328.
Ul-Hamid, A. (2018). A Beginners' guide to scanning electron
microscopy (pp. 4–6). Switzerland: Springer Nature
Switzerland AG.
Vijayakumar, G., Dharmendirakumar, M., Renganathan, S.,
Sivanesan, S., Baskar, G., & Elango, P. (2009). Removal of
Congo red from aqueous solutions by perlite. CLEAN - Soil
Air Water, 37(4–5), 355–364.
Wu, S., Zhao, L., Wang, L., Huang, X., Zhang, Y., Feng, Z., & Cui,
D. (2019). Simultaneous Recovery of Rare Earth Elements
and Phosphorus from Phosphate rock. Phosphoric Acid
Leaching and Selective Precipitation: Towards Green
Process, 37(6), 652–658.
Xu, X., Jiang, X., Jiao, F., Chen, X., & Yu, J. (2018). Tunable
assembly of porous three-dimensional graphene oxide-corn
zein composites with strong mechanical properties for ad-
sorption of rare earth elements. Journal of the Taiwan
Institute of Chemical Engineers, 85, 106–114.
Water Air Soil Pollut (2019) 230:308
Yaoguang, Y. U., Chen, G., Zhou, Y., & Han, Z. (2015). Recent
advances in rare-earth elements modification of inorganic
semiconductor-based photocatalysts for efficient solar energy
conversion: A review. Journal of Rare Earths, 33(5), 453–
462. https://doi.org/10.1016/S1002-0721(14)60440-3.
Youssef, W. M., Hagag, M. S., & Ali, A. H. (2018). Synthesis,
characterization and application of composite derived from
rice husk ash with aluminium oxide for sorption of uranium.
Adsorption Science and Technology, 36(5–6), 1274–1293.
https://doi.org/10.1177/026361741876892.
Youssef, L., Morci, A., & Hagag, M. S. (2019). Uranium ions
adsorption from acid leach liquor using acid cured phosphate
rock: Kinetic, equilibrium and thermodynamic studies.
Separation Science and Technology.
Yu, Z., Meng, X., Zheng, Z., Lu, Chen, H., Huang, C., Sun, H.,
Liang, K., Ma, Z., Qia, Y., & Zhang, T. (2019). Room
temperature multiferroic properties of rare-earth-substituted
Aurivillius phase Bi5Ti3Fe0.7Co0.3O15. Materials Research
Bulletin, 115, 235–241.
Zhao, F., Repo, E., Meng, Y., Wang, X., Yin, D., & Sillanpää, M.
(2016). An EDTA-b-cyclodextrin material for the adsorption
of rare earth elements and its application in preconcentration
of rare earth elements in seawater. Journal of Colloid and
Interface Science, 465, 215–224.
Zhou, J., Yi, Y., Shu, Z., Wang, Y., Yakubu, Y., Zhao, Y., & Li, X.
(2019). Enhancing waterproof performance of phosphogyp-
sum non-fired ceramics by coating silane-coupled unsaturat-
ed polyester resin. Materials Letters, 252, 52–55.
Znajdek, K., Szczecińska, N., Sibiński, M., Wiosna-Sałyga, G., &
Przymęcki, K. (2018). Luminescent layers based on rare
earth elements for thin-film flexible solar cells applications.
Optik, 165, 200–209.
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