Journal of Cleaner Production 211 (2019) 566e573

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Leaching mechanism of ion-adsorption rare earth by mono valence

cation electrolytes and the corresponding environmental impact
Qiuhua Xu a, b, Yuanyuan Sun a, Lifeng Yang a, Cuicui Li a, Xuezhen Zhou a, Weifan Chen a,
Yongxiu Li a, *
a
Research Center for Rare Earths & Micro/Nano-Functional Materials, Nanchang University, Nanchang, Jiangxi, 330031, PR China
b
College of Environmental and Chemical Engineering, Nanchang Hangkong University, Nanchang, Jiangxi, 330063, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Ion-adsorption rare earth (IARE) is a very important resource which is adsorbed on clay mineral surface
Received 23 February 2018 and can be leached by appropriate electrolyte solutions. A comprehensive understanding of the leaching
Received in revised form mechanism is crucial for achieving high extraction efficiency with low cost and less environmental
19 September 2018
impact. In this paper, a series of inorganic electrolytes with different concentrations were employed to
Accepted 11 November 2018
Available online 23 November 2018
leach the IARE, and the relationship between leaching efficiency (LE) of IARE and zeta potential of the
leached clay mineral particles (CMPs) was investigated. A linear relationship between the LE of IARE and
zeta potential of CMPs is observed for every electrolyte. However, the slope (S) of the linear relationship
Keywords:
Ion adsorption rare earths
greatly depends on the type of the cations and follows a sequence of S(NHþ þ þ
4 )＞S(K )＞S(Na ). In addition,

Leaching mechanism in the case of ammonium or potassium ions, the slope is almost the same for both SO2 4 and Cl . But for

Zeta potential sodium ions, a significant difference of slope is observed with the order of S(SO2 4 )＞S(Cl ). These facts
Environmental impact suggest that the cations play a dominating role in affecting the leaching of IARE, while the anions also
Clay mineral contribute to the LE of IARE. Based on the electric double layer model and hydration theory, a leaching
Electric double layer mechanism is proposed to illustrate the dependence of zeta potential on the LE of IARE and the residual
ion concentration in rinsing solutions which is considered to be the main factor influencing the envi-
ronment of mine district. This work may provides a promising route for enhancing the LE and estimating
the environmental impact of remaining electrolytes in mine tailing.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction one. Therefore, a general leaching reaction with ammonium salts

can be expressed as follows (Li, 2014; Chi and Tian, 2006; He et al.,
Ion adsorption rare earth (IARE) is a unique resource with sig- 2016):
nificant commercial value, as it contains almost all the rare earth
elements (REEs), especially the middle and heavy REEs. Therefore, [Al2(Si2O5) (OH)4]mnRE3þ(s)þ3nNHþ
4 (a)#[Al2(Si2O5)
great attention has been paid to its exploitation and applications (OH)4]m3nNHþ 4 (s)þnRE
3þ
(a)
(Li, 2014; Chi and Tian, 2006; Xu et al., 2016; Binnemans et al.,
2013). This type of deposit is formed from long-term weathering where (s) and (a) represent the solid phase and aqueous phase,
process of REEs-containing rocks in warm humid climate under respectively.
chemical, physical, mechanical and biological interactions. It is Various electrolyte solutions containing such cations as Naþ,
generally recognized that leaching IARE is an ion exchange process NHþ þ 2þ 2þ 2þ 3þ
4 , K , Ca , Mg , Fe , Fe , and Al
3þ
can be adopted to leach
of cations in the electrolyte solutions with REEs adsorbed on the IARE. Among them, ammonium sulfate is the most extensively used
clay minerals. The main clay minerals in the deposits are alumi- leaching agent due to its low cost, high yield and high quality (Li,
nosilicates, such as kaolinite, illite, and smectite, etc. Among them, 2014; Chi and Tian, 2006; Xu et al., 2016; Xiao et al., 2015a,b;
kaolinite with composition of [Al2(Si2O5) (OH)4]m is the dominant Moldoveanu and Papangelakis, 2012, 2013). However, the excess
ammonium residue in tailing also exerts seriously negative effect
on the environment. Especially in the in-situ leaching process, the
* Corresponding author. outflow of ammonium leads to severe pollution to the soil, river
E-mail address: yxli@ncu.edu.cn (Y. Li).

https://doi.org/10.1016/j.jclepro.2018.11.112
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573
and underground water near the mine (Xu et al., 2016; Xiao et al.,
2015a,b). In order to develop new techniques for increasing the
LE and reducing the environmental impact originating from the
residual electrolyte ions in tailing, it is of great significance to
elucidate the behavior of different electrolytes in leaching RE and
the underlying leaching mechanism.
It was reported that the leaching ability of different electrolyte
solutions for rare earth depends on the ion exchange capacity of the
electrolyte to rare earth ions, which relies on their relative ionic
potential in the view of hydration theory. In fact, based on the
viewpoint of electrical double layers (EDL) model, a clay mineral
particle (CMP) in aqueous solution is considered to be covered by
water film with EDL structure, which is divided into two parts
separated by a plane (the Stern plane) located at about a hydrated
ion radius from the surface (Crundwell 2016; Shaw, 1992; Tao et al.,
2007). The centers of any specifically adsorbed ions are located in
the stern layer. Ions with centers located beyond the Stern plane
form the diffusion part of the double layer. The outer surface of a
particle motioning in solution is referred to as sliding surface or
shear plane, and the electrical potential difference between the
sliding surface and the particle surface corresponds to zeta po-
tential, which can be obtained by electrokinetic measurement. This
measurement is of significant importance since no direct method is
available to determine the potential of surface and stern layer while
the value of zeta potential is very close to the stern potential and
lower than the surface potential (Sans et al., 2017). In literature,
numerous studies have been conducted to investigate the proper-
ties and zeta potential of inorganic minerals (Au and Leong, 2013;
Zarzycki et al., 2007; Mahrouqi et al., 2017) in aqueous solution.
Furthermore, zeta potential is also a very important parameter to
analyze electrostatic properties of synthesized materials such as
nano-sized or composite materials and to discuss the ion distri-
bution in EDL of colloid materials (Jastrzebska et al., 2016).
However, few literature reported studies on the zeta potential
variation in leaching of IARE (Wang et al., 2017; Zhang et al., 2018).
Moreover, most of the reported zeta potential data only dealt with
the effects of electrolytes and their concentration on the LE and the
swelling characterization of clay minerals. In this study, we focus on
the zeta potential variation of IARE-containing CMPs leached by a
serious of electrolyte solutions and the subsequent water washing
process. Herein, six inorganic salts with monovalence cations were
employed to leach the IARE, and the effects of the type and con-
centration of electrolytes on LE of IARE and zeta potentials of the
leached CMPs in water were investigated. The leaching ability se-
quences of the electrolytes and the corresponding contribution of
their cations and anions were elucidated respectively. Together
with the analysis on released ions in different processes of water
rising, a mechanism based on EDL model was proposed to reveal
the relationship of Zeta potential variation with the LE and the
environmental impact. These results are of great theoretical and
practical significance to further raise the LE of IARE, cut down the
consumption of raw materials (Xiao et al., 2016a), and reduce
environmental impacts (Binnemans et al., 2015).
2. Experimental methods
2.1. Batch leaching tests and measurements
0.001e0.128 mol/L electrolyte solutions ammonium sulfate (AS),
ammonium chloride (AC), sodium sulfate (SS), sodium chloride
(SC), potassium sulfate (PS), and potassium chloride (PC) were
respectively prepared using deionized water and the corresponding
analytical grade reagents.
CMPs containing IARE were sampled from Longnan rare earth
mine (Jiangxi, China) and screened by wet sieving method. CMPs
567
under 800 mesh dried at 100  C were used to meet the re-
quirements for sample uniformity when measuring zeta potential.
Table 1 presents the chemical composition of CMPs used in this
study. As listed in Table 1, alumina and silica constitute the majority
of CMPs, while iron oxide, potassium oxide, magnesium oxide, ti-
tanium oxide and other elements account for the minority of CMPs.
The loss on ignition values indicated that CMPs contain lower
carbonaceous substances but higher mineral matters, which are
excellent natural adsorbents for metal ions.
In each leaching test, 5 g of CMPs sample and 100 ml leaching
agent solution were mixed in 250 ml Erlenmeyer flasks with rubber
stoppers. The flasks were placed into a thermostatic oscillating tank
and shaked at 30  C for 1 h to reach leaching equilibrium. After
solid-liquid separation by filtration, the collected solution was
employed to determine the concentrations of rare earth ions and
electrolyte ions, such as ammonium and sulfate ions. The concen-
trations of the rare earth in the filtrates were analyzed by arsenazo
III spectrophotometry. The determination procedure is as follows: A
certain amount of filtrate (containing 4e20 ìg REE) was mixed with
10 ml of acetic acid-sodium acetate buffer solution (pH 3.3) and
2 ml chromogenic agent (0.25 wt% arsenazo Ⅲ), and then diluted to
50 ml with deionized water. After the solution was well shaken and
rested for more than 15 min, the absorbance of the solution was
determined at 655 nm wavelength using a blank reagent as refer-
ence. The concentration of RE in the subsequent solution was
calculated based to the plotted the standard curve with the linear
correlation coefficient of 0.998 and the linear concentration range
of 5e25 ppm. The LE of IARE was calculated based on the rare earth
concentrations in the filtrates and the contents in CMPs.
ðCl  Vl Þ
LEð%Þ ¼  100%
W  Cs
where LE is the leaching efficiency of IARE (%), Cl is the concen-
tration of RE in leaching solution (calculated as rare earth oxide,
REO, g/ml), Vl is the volume of the leaching solution (100 ml), W is
the sample weight (5 g), Cs is the RE content in CMPs sample
(determined previously by full leaching method, 0.103% calculated
as REO) (Li, Y.X., 2014). The determination error of LE is mainly from
colorimetric analysis. The relative error of RE concentration is less
than 13%, and the relative error range of LE is less than 10%.
Meanwhile, the collected CMPs leached by different electrolyte
solutions (named as CMPs-Ld) were re-dispersed into 250 ml
deionized water and subjected to Zeta Potential analysis. The Zeta
Potentials of CMPs and CMPs-Ld were measured by ZetaProbe
(Colloidal Dynamics, USA) (system error ±0.9mv). The measure-
ment was conducted at room temperature by selecting the rota-
tional speed of 200 r/min, using water as solvent (dielectric
constant 78, density 1 g/ml, viscosity 8904 cP). The density, particle
mass fraction, and dielectric constant of CMPs were set at 2.6 g/ml,
2% and 2. The experimental error of Zeta potential is ±0.9 mV for
the same sample, and is enlarged to ± 1e2 mV for different exper-
iments under the same condition.
After filtration, the collected solid samples were re-dispersed
into another 250 ml deionized water for the second rinsing. The
Zeta Potential of CMPs as well as the contents of ammonium and
sulfate in the rinsing solutions were determined. The above pro-
cesses were repeated 6e7 times. The contents of ammonium and
sulfate in the rinsing solutions were determined. The concentra-
tions of ammonia were determined using Nesster's reagent color-
imetry. The determination procedure is as follows: In a colorimetric
tube, a certain amount of filtrate was well mixed with 1.0 mL po-
tassium sodium tartrate solution and 1.5 mL Nessler reagent solu-
tion, then diluted to 50 ml with deionized water. After the solution
was well shaken and rested for more than 10 min the absorbance of
568 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573
Table 1
Chemical composition of clay mineral particles (CMPs) under 800 mesh.
Composition SiO2 Al2O3 Fe2O3 FeO CaO
(% weight) 50.98 29.61 3.97 0.34 0.011
the solution was determined at 420 nm wavelength using a blank
reagent as reference. The standard curve of absorbance vs the
ammonia nitrogen concentration was plotted with R2 of 0.999 and
the linear concentration range of 5e100 ppm. The relative error of
ammonium concentration is less than 8%.
The concentrations of sulfate were determined using spectro-
scopic barium turbidity method. The determination procedure is as
follows: A certain amount of filtrate was injected into a 50 mL
volumetric flask, and diluted to the scale with deionized water, and
then poured into a 250 mL cone bottle. To this solution, 5 mL of the
conditional reagent and 0.5 g solid BaCl2 were added quickly. After
1 min agitation and 6 min resting, the absorbance of the solution
was determined at 420 nm wavelength. The above mentioned
conditional reagent was previously prepared by dissolving 30 g of
sodium chloride with 200 mL water, 190 mL 95% alcohol, 75 mL
glycerol, 30 mL concentrated hydrochloric acid, and then diluting it
to 500 m and final intense shaking. The concentration of sulfate was
calculated based on the standard curve of absorbance vs concen-
tration with a Linear range of 2e80 ppm. The relative error of sul-
fate concentration is less than 10%.
Following the same procedure as above mentioned, more
leaching and immersion experiments were carried out using 6
electrolytes with 7 set of concentrations (0.004, 0.008, 0.016, 0.032,
0.064, 0.096, 0.128 mol/l). The names of the collected clay mineral
particles samples leached by AS, AC, SS, SC, PS, PC are shortened as
CMPs-Ld-AS, CMPs-Ld-AC, CMPs-Ld-SS, CMPs-Ld-SC, CMPs-Ld-PS,
and CMPs-Ld-PC, respectively.
2.2. Model and leaching mechanism
According to the EDL model, a mechanism is proposed to
elucidate the leaching process of IARE and discuss the effect of both
anion and cation on the LE of IARE and the environment. The EDL
model is adopted mainly because it is the simplest model and can
offer a qualitative and quantitalive analysis on all available
adsorption data. The adsorption and desorption of ions on CMPs
can be represented by coulombic term calculated from the Goug-
Chapman EDL model (Plaza and Ontiveros-Ortega et al., 2015):
P ¼ expðF j=RTÞ
Where F represents the molar Farady constant, R is the molar
gas constant. T is the absolute temperature, Jis the electrostatic
potentials. The surface of CMP is negatively charged, including the
constant negative face charge responsible for the isomorphic sub-
stitutions within tetrahedral and octahedral sheets, and the pH-
dependent edge charge generated by the breakage of Al octahe-
dral in edge surface or hydroxides on the edge proton adsorption/
desorption reactions (Xu et al., 2018).
As shown in Fig. 1, the zeta potential of IARE-containing CMPs
suspension is less negative value (A), suggesting that the amount of
RE ions specifically adsorbed on the surface of CMP is not sufficient
to neutralize the surface charge, while some weakly adsorbed low
valance ions in SL migrated beyond the sliding plane and resulted in
negative zeta potential. Adding electrolyte ions into this suspension
will result in an ion exchange process, in which the RE ions in SL are
replaced by electrolyte ions and migrated from SL to DL (B); After
filtration, CMPs containing electrolyte ions are separated from RE
ions (C). When re-dispersing these CMPs in water, the electrolyte
MgO K2O Na2O TiO2 P2O5 MnO Loss on ignition
0.27 3.36 0.082 0.11 <0.01 0.036 10.65
ions adsorbed in SL will enter the DL, resulting in a large negative
zeta potential (D). Therefore, the zeta potential of CMPs can in-
dicates the amount of electrolyte ions in SL and their ability to enter
the DL, which can be demonstrated via the analysis of electrolyte
ions in the solution.
3. Results and discussions
3.1. Effects of electrolyte type and concentration on the LE of IARE
The dependence of LE on the electrolyte concentration is dis-
played in Fig. 2. For each electrolyte, the LE of IARE grows up with
the increasing electrolyte concentration, which is well consistent
with most of the previous reported results (Li, 2014; Chi and Tian,
2006; Xu et al., 2016). An apparent difference in the LE of IARE is
also observed for different electrolytes with the same concentra-
tion. For example, at concentration of 0.064 mol/L, the LE of IARE
follows a sequence of AS > AC > PS > PC > SS > SC. In terms of the
influence of anion and cation on the LE of IARE, the order is as
follows: NHþ þ þ 2 
4 > K > Na and SO4 > Cl . The cations make a greater
influence than anions. Specifically, at low concentrations, the LE of
IARE by potassium sulfate is higher than that by ammonium chlo-
ride. On the contrary, with the further increase of electrolyte con-
centration, the LE of IARE by ammonium chloride is obviously
higher than that by potassium sulfate, These facts indicate that the
LE of IARE is dominated by cations, and the influence of sulfate
concentration on the LE of IARE in low concentration region is more
obviously than in high concentration region. The ammonium has
greater contribution to the LE of IARE in high concentration region
is generally explained by its larger ionic potential and smaller
radius of hydrate ion than potassium and sodium ions; However,
the radius of ammonium hydrate ion is not much larger than that of
potassium hydrate ion. Thus, some other reasons must underline
the fact that the LE of IARE by ammonium salt electrolyte is obvi-
ously larger than that by potassium ion, such as ion strength, the
coordination of anions with cations and the weak interaction be-
tween the ion and clay surface. It is the most important thing that
ammonium ions have the ability to form hydrogen bonds with the
oxygen atom on the surface of CMPs. It is the hydrogen bond
interaction between ammonium ion and oxygen atoms on the
surface of mineral particles that makes the adsorption ability of
ammonium ions on clay surface stronger than that of potassium
and sodium ions. Meanwhile, the enhancement range of LE of IARE
by potassium ion is getting smaller and smaller with the growing
concentration of potassium ion in high concentration regions,
which is attributed to the formation of compound salts including
potassium rare earth sulfate and potassium aluminum sulfate
compound salt.
3.2. Relationship between the LE of IARE and zeta potential of
CMPs-Ld
Fig. 3 shows the zeta potential of all CMPs-Ld samples re-
dispersed in water. The negative value of zeta potential is attrib-
uted to the diffusion of cations from SL into DL. Compared to Fig. 2,
in addition to the abnormal elevation of sodium sulfate and sodium
chloride in the high concentration region, the relationship between
zeta potential and electrolyte concentrations is very similar to that
 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573
Fig. 1. Leaching mechanism of IARE by ammonium sulfate (a, b, c) based on the EDL model and the comparison of zeta potential (x) of CMPs (a) and CMPs-Ld (d) in water; (SL: stern
layer; DL: Diffusion layer; 4: Surface potential of particle).
between the LE of IARE and electrolyte concentration, implying that
the zeta potential is related to the LE of IARE.
Specifically, as to each investigated electrolyte, the absolute zeta
potential grows up with the increase of electrolyte concentration.
However, the absolute zeta potentials for different electrolytes with
the same concentration are different, and follows the order of
AS > AC z PS > SS z SC > PC for electrolyte concentration at
0.064 mol/L, and AS > SS z SC > AC z PS > PC for electrolyte con-
centration at 0.128 mol/L. This result indicates that cations and
anions make different contribution to the enhancement of absolute
zeta potential value and LE of IARE. The order of absolute zeta
potential value is as follows: NHþ þ
4 > Na >K
þ
and SO2 
4 > Cl .
Compared with the sequence of the LE of IARE, the difference lies
between the monovalent alkali metal cations.
So far, enormous effort has been devoted to the research of
leaching IARE, and the hydration theory based on electrostatic
interaction is often used to explain the order of leaching RE by
various electrolytes (Li, 2014; Chi and Tian, 2006; He et al., 2016; Jia,
569
1987; Hu et al., 2017). It is often considered that the ability of cat-
ions diffusing into SL to exchange rare earth ions depends on the
ability of these ions to be adsorbed by the particle surface. Thus, the
exchange capacity for RE ions by different electrolytes relies on the
ionic potential of the hydration cations. It has been suggested that
the LE of IARE by different monovalent cation electrolytes is related
to the ionic radius of a hydrated cation because the ions moving in
aqueous solution and adsorbed on the particle surface are all in the
form of hydrated ions.
The order of crystal radii is generally opposite to the order of the
hydrated ionic radii. For example, the crystal radii of NHþ þ þ
4 , Na , K ,
 2
Cl , SO4 are 1.48 Å, 0.95 Å, 1.33 Å, 1.94 Å, and 2.15 Å, while their
hydrated ion radii are 3.31 Å, 3.58 Å, 3.32 Å, 3.32 Å, and 3.00 Å,
respectively (Jia 1987; Nadine et al., 2013; Nightingale, 1959). The
order of radii for hydrated ions is as follows: NHþ þ þ
4 ˂ K ˂ Na for

cations, and SO24 ˂ Cl for anions. The sequence is opposite to that
of the LE of IARE, indicating that the RE leaching process is domi-
nated by the hydrated ionic radii or ionic potential.
570 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573

The relationship between the LE of IARE and the zeta potential

Fig. 2. The dependence of electrolyte concentration on the LE of IARE by different
electrolytes.
Fig. 3. The dependence of zeta potential of CMPs-Ld on the LE of IARE by different
electrolytes.
Fig. 4. Dependence of the LE of IARE and the zeta potential of CMPs-Ld for different
electrolytes.
of CMPs-Ld for different electrolytes is revealed in Fig. 4. A linear
relationship can be observed for every electrolyte. This correlation
is reported for the first time. Although there are some data about
zeta potential in the literature (Wang et al., 2017; Zhang et al.,
2018), no linear relationship has been found. The main reason is
that the zeta potential measured in the past is mainly the zeta
potential of leaching equilibrium. Because of the influence of high
concentration of electrolyte, it is difficult to reflect the ion distri-
bution of electrolyte on the surface of clay mineral particles.
Furthermore, it is observed that the slopes are different and
depend on the cations and anions. The largest slope was observed
for ammonium ion ranging from 5.7 to 5.8, followed by potas-
sium ion of 3.9 to 4.1. The smallest slope corresponds to sodium
ion from 1.2 to 2.7. These data show that the dependence of LE of
IARE on the zeta potential of CMPs-Ld is dominated by cations and
follows the sequence of S(NHþ þ þ
4 )＞S(K )＞S(Na ). The slope values
are almost the same for AS and AC, PS and PC, respectively. A sig-
nificant effect of the anions on the slope of the linear relationship
between LE of IARE and zeta potential is only observed for SS and
SC, owing to the weak adsorption ability of sodium ion toward
CMPs, which is not beneficial for leaching rare earth but increases
the absolute zeta potential.
As reported previously (Li, 2014; Anastopoulos et al., 2016; Callura
et al., 2018; Xiao et al., 2016b; Uddin, 2017), the adsorption of cations
on the surface of CMPs belong to physical adsorption process, they are
attracted each other by charge interaction without chemical bonding
formation. However, the adsorption of trivalent rare earth ions on the
surface of clay mineral particles is in agreement with the Langmuir
adsorption isotherm equation, which belongs to the monolayer
adsorption. Nevertheless, the univalent ions such as ammonium,
sodium, and potassium ions are not consistent with the Langmuir
adsorption isotherm equation, appliable to the multilayer weak
adsorption. Therefore, as shown in Fig. 1(A), RE ions adsorbed on the
surface of CMPs lie mainly in SL. The ions in SL can diffuse to DL
through thermal motion. The lower the valance of an ion leads to
easier diffusion of the ion. Therefore, the RE ions distributed in SL are
difficult to be leached by water, since they are trivalant ions and are
tightly adsorbed on the particle surface. In general, the real adsorption
capacity of CMPs for RE is less than the saturated adsorption capacity
of CMPs. Thus, many low valance ions such as Naþ and Kþ, are
adsorbed together with RE ions on the surface of CMP. These low-
valence ions enter into DL from SL when CMPs are dispersed in wa-
ter, resulting in negative zeta potential value of CMPs. The higher
content of RE ions is, the lower negative zeta potential value is.
In general, the cations with smaller hydrated radii exhibit higher
LE of IARE. However, the previous work failed to explain why the
anions with smaller hydrated radii also present higher LE of IARE.
As for the role of anions in RE leaching process, the previous typical
interpretation is that the sulfate ions can form more stable com-
plexes with RE ions (Moldoveanu and Papangelakis, 2012, 2013).
However, no detailed illustration has been proposed.
In our present study, the hydration theory of anions is adopted
to interpret the much higher LE of IARE by sulfate than by chloride.
On one hand, sulfate anion has two negative charges, and is smaller
than chloride ion in terms of hydrated ion radius. The ionic po-
tential (Z2/r) of hydrated sulfate is much higher than that of chlo-
ride. On the other hand, although the CMPs are negatively charged,
there exist some positively charged regions on the edge surface of
mineral particles due to surface bond rupture (Xu et al., 2018).
Toward these areas, the negatively charged anions are attached.
Thus, higher ionic potential of negative charge helps the anions to
be adsorbed, leading to more negative charges on the particle
surface and more cations into the SL for charge conservation, which
in turn promotes the leaching of RE ions.
 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573
3.3. The zeta potential and residual ions concentration of CMPs-Ld-
AS
In the previous studies on ion adsorbed rare earth, few people
paid attention to the quantity and characteristics of residual elec-
trolytes in tailings. According to EDL model, the zeta potential can
reflect the type and concentration level of counter-ions in SL on the
surface of particles when re-dispersed in water due to their
different migrating ability from SL to DL, as shown in Fig. 1 (d). In
order to verify that the residual ion concentration on the surface of
CMPs-Ld-AS is higher than CMPs-Ld-AC, and to evaluate the impact
of the residual ions in tailing on environment, the obtained CMPs-
Ld-AS and CMPs-Ld-AC were respectively rinsed with water for 5e7
times. In each rinsing process, the zeta potential of the particles and
the concentration of ions in the filtrates were determined, and then
the filtrated solid was subjected to the next rinsing. The zeta po-
tential of CMPs-Ld-AS and the corresponding ammonium concen-
tration in the rinsing filtrate as a function of rinsing times are
presented in Fig. 5. It can be seen that the negative zeta potential of
CMPs-Ld-AS increases with the increase of ammonium sulfate
concentration and decreases with the increase of rinsing times.
As shown in Fig. 5(a), on the first rinsing stage, the zeta potential
of CMPs-LD-AS ranges from 9 to 24 mV, the absolute value of
zeta potential for CMPs-Ld increases with the increase of the con-
centration of AS, demonstrating that the ammonium ions in the SL
of CMPs-Ld-AS increases, and leads to the increasing of LE. In the
second and third rinsing stages, the zeta potential ranges from 6
to 15 mV, and 5 to 12 mV respectively. After the sixth and
seventh rinsing stages, the zeta potential of each sample shows
little variation, but still increases with the increase of AS concen-
tration. In fact, the required rinsing times to achieve a stable zeta
potential value increases with the increase of AS concentration.
As shown in Fig. 5(b), the dependence of ammonium concen-
tration in the rinsing solution on the rinsing times is similar to the
zeta potential as shown in Fig. 5(a). The difference lies in the decline
rate with the rinsing times. The concentration difference is signif-
icant on the first two rinsing stages, and then becomes stable after
two rinsing cycles. The fact that the ammonium concentration in
the first rinsing solution is much higher than the following rinsing
solution demonstrates that the ammonium ions adsorbed in SL are
easy to wash out by a simple water rinsing process. The propor-
tional relationship between the LE and the amount of ammonium
washed out indicates that the leaching of RE ions depends on the
amount of electrolyte cation in the SL.
After 6 or 7 times of water rinsing, the samples were leached
with 10% NaCl solution followed by water rinsing. The zeta po-
tential and ammonium concentration in the leaching solution were
determined and shown in Figs. 5 and 6. It was found that the
Fig. 5. Zeta potential of CMPs-Ld-AS (a) and ammonium concentration (b) via the rinsing times.
571
remaining ammonium in CMPs-Ld-AS after rinsing for 6 or 7 times
is very little, indicating that the sodium ions remaining in the
CMPs-Ld can be removed more easily.
As shown in Table 2, the dependence of sulfate concentration in
the rinsing solution on rinsing times is similar to ammonium in
Fig. 6 (B). The concentration difference is significant for the first two
rinsing stages. Unlike ammonium, after two water-rinsing cycles,
the content of sulfate ions is lower than the detection limit, sug-
gesting that the sulfate ions are easier to be removed than
ammonium. The result can also be rationalized by the proportion of
ammonium to sulfate. The calculated molar ratio of ammonium to
sulfate is less than the stoichiometric ratio of ammonium sulfate in
the first rinsing solution. However, this ratio becomes very large,
and even no sulfate can be detected in the second rinsing solutions
of CMPs-LD-SS and CMPs-LD-PS.
The concentrations of sulfate both in the leaching and rinsing
solutions of CMPs-LD-AS are lower than that of CMPs-LD-SS and
CMPs-LD-PS, indicating that more sulfate ions are adsorbed to the
surface of CMPs-LD and fewer are washed out. Meanwhile, when
leaching with high concentration of sulfate, some sulfate ions were
detected in the second rinsing solution of CMPs-LD-AS, but no
sulfate ions was detected in the cases of CMPs-LD-SS and CMPs-LD-
PS. This fact indicates that the sulfate adsorbed onto the CMPs-LD-
AS is more difficult to be washed out than CMPs-LD-SS and CMPs-
LD-PS. Hence, the high leaching effect of ammonium sulfate on RE
can be interpreted as the synergistic adsorption between ammo-
nium cation and sulfate anion.
3.4. The zeta potential and residual ion concentration of CMPs-Ld-
AC
Using above mentioned method, ammonium chloride solutions
with different concentrations were used to leach CMPs, and the
surface zeta potential and ammonium concentration in the leach-
ing and rinsing solutions were determined. As shown in Fig. 6, the
zeta potential of CMPs-Ld-AC and the ammonium concentration in
the rinsing solution have similar variation trend to that of CMPs-Ld-
AS. However, the magnitude of zeta potential and ammonium
concentration are relatively lower, and the decrease rate as a
function of rinsing times is faster, especially for the first 1 to 2 times
of rinsing.
Compared to AS, the required rinsing times to reach a stable zeta
potential value is less. Therefore, the higher LE of IARE in sulfate
medium can be attributed to more ammonium ions adsorbed on
the SL of CMPs, which results in slightly higher absolute zeta
potential.
As mentioned above, the negative zeta potential value is
ascribed to the diffusion of cations from SL into the DL. However, in
572 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573

Fig. 6. Zeta potential of CMPs-Ld-AC (a) and ammonium concentration (b) via the rinsing times.

Table 2
Sulfate content (ppm) in leaching and rinsing solutions of CMPs-Ld-AS, SS, PS.

CMPs-Ld-AS Leaching solution 189 358 627 1572 3197 5200 6695
1st rinsing solution 4.98 12.22 22.19 32 75 113 139
2th rinsing solution 0 0 0 0 0.62 2.05 1.22
CMPs-Ld-SS Leaching solution 220 430 880 1730 3350 5140 7170
1st rinsing solution 4 11 23 49 96 131 167
2th rinsing solution 0 0 0 0 0 0 0
CMPs-Ld-PS Leaching solution 202 418 822 1668 3218 5002 7084
1st rinsing solution 3.62 9.79 22.33 43.66 83.7 139.3 169.2
2th rinsing solution 0 0 0 0 0 0 0

the water rinsing process of CMPs-Ld, the anions in SL will shift into
DL as well, offsetting the negative potential and leading to an
opposite result. The fact that the zeta potential variation in the
rinsing process increases with the increase of ammonium indicates
that the sulfate can carry more ammonium ions into SL. The slow
release rate of ammonium ions in the leaching process also proves
that the presence of sulfate can drive more ammonium to SL,
leading to a slower release rate of ammonium ion in the rinsing
process.
Similarly, after 5-time water rinsing, the CMPs-Ld-AC samples
were leached with 10% NaCl solution and followed by another
water rinsing. The zeta potential value of CMPs-Ld-AC and the
ammonium concentration in leaching solution were also deter-
mined. The results in Fig. 6 demonstrate that after AC leaching, the
amount of residual ammonium in tailing is less than that using AS
as leaching agent, and can also be completely washed out in the
subsequent rinsing process.
3.5. Environmental impact and the corresponding solutions
The assessment of environmental impact plays an important
role in the construction of a better ecological environment.
Therefore, all industries attach great importance to the environ-
mental impact of the strategy process, and propose effective solu-
tions based on these impacts (Chen et al., 2017; Ramírez-Guinart
et al., 2018; Samal et al., 2015). The excess ammonium residue in
tailing also exerts negative effect on the environment (Lee and
Wen, 2017; Zaimes et al., 2015). The environmental impact of
leaching IARE by monovalent cation electrolytes is mainly man-
ifested in two aspects. The first is the generation of a large amount
of wastewater (Xu et al., 2016). As discussed above, the residual
ammonium sulfate in tailing can be washed out by water such as
rainwater. Based on the results of the first rinsing process, to ensure
that the ammonium content in the wastewater from tailing is less
than 15 mg/L, the amount of water needed is 50 times the amount
of tailing, and the concentration of ammonium sulfate used in
leaching RE should not be higher than 0.032 mol/L. However, the
concentration of ammonium sulfate used in the actual production
is over 0.032 mol/L. That is to say, after the leaching of rare earths,
the volume of wastewater derived from the tailing rainwater
should be 50 times more than that of tailing. Given the content of
an IARE deposit is around 0.08 wt% and a recovery rate of 80%, the
wastewater produced from manufacturing of 1000 kg REOs is
estimated to be over 78125 M3.
Another serious consequence is the risk of tailing landslide and
collapse. The tailing is composed of clay particles with a large
amount of ammonium sulfate. The negative zeta potential is
directly proportional to the amount of residual ammonium, leading
to landslide in raining conditions due to the repulsion between the
particles. The high absolute zeta potential of CMPs-Ld means that
there exists a large repulsive force between the particles, which
enables the particles to slip from each other more easily and lower
the stability of the ore body, causing debris flow and collapse in
IARE mines.
To overcome these challenges, one direct approach is the timely
removal of the electrolytes in tailing. As shown in Fig. 6, filling
water to tailing is indispensable for reducing the surface zeta po-
tential of CMPs and enhancing the seam stability. However, this
method is not suitable for in-situ leaching, due to the difficulty of
water recycling. Nevertheless, it is applicable to heap leaching
mining. Another promising method is to replace the electrolyte of
ammonium by a high valence cation leaching agent, such as sulfates
of aluminum (Xu et al., 2018; Yang et al., 2018), ferrous (Xiao et al.,
2016c) and magnesium (Xiao et al., 2015c). Especially in the case of
aluminum sulfate, the electrolyte in tailing is not easy to be water
leached and the zeta potential of minerals can be controlled to a
very low level. For the second method, we have proposed some
novel techniques to leach IARE with aluminum sulfate solution. The
solution can be prepared from the raffinate of leaching solutions of
aluminum containing slug, from which rare earths have been
recovered by solvent extraction (Li et al., 2016).
 Q. Xu et al. / Journal of Cleaner Production 211 (2019) 566e573
4. Conclusions
The LE of IARE by six electrolytes with different concentrations
was comparatively investigated as a function of the zeta potential of
CMPs-Ld. It is found that there exists linear relationship between
the LE of IARE and the negative zeta potential of CMPs-Ld, and that
the slope (S) of the linear relationship is highly dependent on the
type of the cations, following the sequence of S(NHþ 4 )＞S(K )＞
þ Li, Y.X., 2014. Ion Adsorption Rare Earths and Their Green Extraction. Chemical
þ 2
S(Na ). However, the slope is almost the same for both SO4 and
Cl in the case of ammonium or potassium ions, indicating that the
contribution of anions to the LE of IARE and the zeta potential is
synchronous. A significant slope difference was observed with the

order of S(SO2 4 )＞S(Cl ) for sodium ions, indicating that the
contribution of sulfate to the LE is more obvious in the case of so-
dium ion due to its weak affinity to clay minerals. These results
show that the cations play a dominant role in the leaching of IARE
and follow the sequence of NHþ þ þ
4 ＞K ＞Na . Moreover, the anions
also contribute to the leaching of IARE, especially for SO24 .
Based on the EDL model and hydrate theory, the leaching ability
sequence and its relationship with zeta potential are well illus-
trated combined with the analysis on residual ion concentration in
rinsing solutions. Although ammonium sulfate can be considered
as the most effective leaching agents among the electrolytes tested
here, the deficiency of ammonium sulfate as a leaching agent is also
obvious because ammonium is easy to be desorbed from tailing,
leading to the huge release of ammonium-containing wastewater
and the occurrence of landslides due to the resulting large absolute
value of zeta potential. In summary, these results open up new
avenues for the development of new leaching techniquew,
addressing the problem of low LE of RE and reducing serious
environmental pollution.
Acknowledgments
This work is financially supported by the National Natural Sci-
ence Foundation of China (21261014, 51274123) and the National
Key Basic Research Development Program of China
(2012CBA01204).
References
Anastopoulos, I., Bhatnager, A., Lima, E.C., 2016. Adsorption of rare earths: a review
of recent literature. J. Mol. Liq. 221, 954e962.
Au, P.I., Leong, Y.K., 2013. Rheological and zeta potential behaviour of kaolin and
bentonite composite slurries. Colloids Surf., A: Physcochem Eng. Aspects 436,
530e541.
Binnemans, K., Jones, P.T., Blanpain, B., Gerven, T.V., Pontike, Y., 2015. Towards zero-
waste valorisation of rare-earth-containing industrial process residues: a crit-
ical review. J. Clean. Prod. 99, 17e38.
Binnemans, K., Jones, P.T., Blanpain, B., Van Gerven, T., Yang, Y., Walton, A.,
Buchert, M., 2013. Recycling of rare earths: a critical review. J. Clean. Prod. 51,
1e22.
Chen, X., Huang, G., An, C., Yao, Y., Zhao, S., 2017. Emerging N-nitrosamines and N-
nitramines from amine-based post-combustion CO2 capture-A review. Chem.
Eng. J. 335, 921e935.
Chi, R.A., Tian, J., 2006. Hydrometallurgy of the Weathered Crust Elution-deposited
Rare Earth Ores. Science Press, Beijing (In Chinese).
Crundwell, F.K., 2016. The mechanism of dissolution of minerals in acidic and
alkaline solutions: prat V surface charge and zeta potential. Hydrometallurgy
161, 174e184.
Callura, J.C., Perkins, K.M., Noack, C.W., Washburn, N.R., Dz, D.A., 2018. Selective
adsorption of rare earth elements onto functionalized silica particles. Green
Chem. 20, 1515e1526.
He, Z.Y., Zhang, Z.Y., Yu, J.X., Zhou, F., Xu, Y.L., Xu, Z.G., Chen, Z., Chi, R.A., 2016.
Kinetics of column leaching of rare earth and aluminum from weathered crust
elution-deposited rare earth ore with ammonium salt solutions. Hydrometal-
lurgy 163, 33e39.
Hu, G.H., Feng, Z.Y., Dong, J.S., Meng, X.L., Xiao, Y.F., Liu, X.S., 2017. Mineral prop-
erties and leaching characteristics of volcanic weathered crust elution-
deposited rare earth ore. J. Rare Earths 35 (9), 906e910.
Jastrzebska, A.M., Karcz, J., Letmanowski, R., Zabost, D., Ciecierska, E., Zdunek, J.,
Karwowska, E., Sielierski, M., Olszyna, A., Kunicki, A., 2016. Synthesis of the
573
RGO/Al2O3 core-shell nanocomposite flakes and characterization of their
unique electrostatic properties using zeta potential measurements. Appl. Surf.
Sci. 362, 577e594.
Jia, Y.Q., 1987. Quantum chemical studies on the hydrated ions of the rare earths.
Inorg. Chim. Acta. 133 (2), 331e336.
Li, Y.X., Yang, L.F., Li, C.C., Xu, Q.H., Zhang, L., Wang, Y., Zhou, X.M., Zhou, X.Z.,
Liu, Y.Z., Li, J., 2016. Method for the high efficiency leaching of ion adsorption
rare earths using aluminium sulfate as leaching reagent. Chin. Patent.
CN201610821052.4.
industry press, Beijing (In Chinese).
Lee, J.C.K., Wen, Z.G., 2017. Rare earths from mines to metals: comparing environ-
mental impacts from China's main production pathways. J. Ind. Ecol. 21 (5),
1277e1290.
Mahrouqi, D., Vinogradov, J., Jackson, M.D., 2017. Zeta potential of artificial and
natural calcites in aqueous solution. Adv. Colloid Interface Sci. 240, 60e76.
Moldoveanu, G.A., Papangelakis, V.G., 2012. Recovery of rare earth elements
adsorbed on clay minerals: I. Desorption mechanism. Hydrometallurgy 117e118
(4), 71e78.
Moldoveanu, G.A., Papangelakis, V.G., 2013. Recovery of rare earth elements
adsorbed on clay minerals: II. Leaching with ammonium sulfate. Hydrometal-
lurgy s131e132 (1), 158e166.
Nadine, S., Horinek, D., Netz, R.R., 2013. Anionic and cationic Hofmeister effects on
hydrophobic and hydrophilic surfaces. Langmuir 29, 2602e2614.
Nightingale, E.R., 1959. Phenomenological theory of ion solvation. Effective radii of
hydrated ions. J. Phys. Chem. 63 (9), 1381e1387.
Plaza, I., Ontiveros-Ortega, A., Calero, J., Aranda, V., 2015. Implication of zeta potential
and surface free energy in the description of agricultural soil quality: effect of
different cations and humic acids on degraded soils. Soil Tillage Res. 146, 148e158.
Ramírez-Guinart, O., Salaberria, A., Vidal, M., Rigol, A., 2018. Dependence of
samarium-soil interaction on samarium concentration: implications for envi-
ronmental risk assessment. Environ. Pollut. 234, 439e447.
Sans, B.E., Guven, O., Esenli, F., Celik, M.S., 2017. Contribution of cations and layer
charges in the smectite structure on zeta potential of Ca-bentonites. Appl. Clay
Sci. 143, 415e421.
Shaw, D.J., 1992. Introduction to Colloid and Surface Chemistry, fourth ed. Butter-
worth-Heinemann, pp. 174e199.
Samal, S., Ray, A.K., Bandopadhyay, A., 2015. Characterization and microstructure
observation of sintered red mud-fly ash mixtures at various elevated temper-
ature. J. Clean. Prod. 101, 368e376.
Tao, H., Xu, R., Tiwari, D., Zhao, A.Z., 2007. Interaction between electrical double
layers of soil colloids and Fe/Al oxides in suspensions. J. Colloid Interface Sci.
310 (2), 670e674.
Uddin, M.K., 2017. A review on the adsorption of heavy metals by clay minerals,
with special focus on the past decade. Chem. Eng. J. 308, 438e462.
Wang, L., Liao, C.F., Yang, Y.M., Xu, H.B., Xiao, Y.F., Yan, C.H., 2017. Effects of organic
acids on the leaching process of ion-adsorption type rare earth ore. J. Rare
Earths 35, 1233e1238.
Xiao, Y.F., Feng, Z.Y., Hu, G.H., Huang, L., Huang, X.W., Chen, Y.Y., Li, M.L., 2015a.
Leaching and mass transfer characteristics of elements from the ion-adsorption
type rare earth ore. Rare Met. 34 (5), 357e365.
Xiao, Y.F., Liu, X.S., Feng, Z.Y., Huang, X.W., Huang, L., Chen, Y.Y., Wu, W.Y., 2015b.
Role of minerals properties on leaching process of weathered crust elution-
deposited rare earth ore. J. Rare Earths 33 (5), 545e552.
Xiao, Y.F., Feng, Z.Y., Huang, X.W., Huang, L., Chen, Y.Y., Wang, L.S., Long, Z.Q., 2015c.
Recovery of rare earths from weathered crust elution-deposited rare earth ore
without ammonia-nitrogen pollution: I. Leaching with magnesium sulfate.
Hydrometallurgy 153, 58e65.
Xiao, Y.F., Feng, Z.Y., Huang, X.W., Huang, L., Chen, Y.Y., Liu, X.S., Wang, L.S.,
Long, Z.Q., 2016a. Recovery of rare earth from the ion-adsorption type rare
earth ore: II. Compound leaching. Hydrometallurgy 163, 83e90.
Xiao, Y.F., Huang, L., Long, Z.Q., Feng, Z.Y., Wang, L.S., 2016b. Adsorption ability of
rare earth elements on clay minerals and its practical performance. J. Rare
Earths 34 (5), 543e548.
Xiao, Y.F., Feng, Z.Y., Hu, G.H., Huang, L., Huang, X.W., Chen, Y.Y., Long, Z.Q., 2016c.
Reduction leaching of rare earth from ion-adsorption type rare earths ore with
ferrous sulfate. J. Rare Earths 34 (9), 917e923.
Xu, Q.H., Yang, L.F., Zhang, L., Li, C.C., Wang, D.S., Zhou, X.M., Zhou, X.Z., Li, Y.X., 2018.
Classification and high Efficient leaching of ion adsorption rare earth based on
its pH dependence. Chin. J. Inorg. Chem. 34 (1), 112e122.
Xu, Q.H., Sun, Y.Y., Zhou, X.Z., Liu, Y.Z., Li, J., Li, Y.X., 2016. Green extraction of ion-
adsorption rare earth resources. J. Chin. Soc. Rare Earths (in Chin.) 34 (6),
650e660.
Yang, L.F., Wang, D.S., Li, C.C., Sun, Y.Y., Zhou, X.Z., Li, Y.X., 2018. Searching for a high
efficiency and environmental benign reagent to leach ion-adsorption rare earths
based on the zeta potential of clay particles. Green Chem. 20, 4528e4536.
Zaimes, G.G., Hubler, B.J., Wang, S., Khanna, V., 2015. Environmental life cycle
perspective on rare earth oxide production. Acs Sustain. Chem. Eng. 3 (2),
237e244.
Zarzycki, P., Szabelski, P., Piasecki, W., 2007. Modelling of z-potential of the mont-
morillonite/electrolyte solution interface. Appl. Surf. Sci. 253, 5791e5796.
Zhang, Z.Y., He, Z.Y., Zhou, F., Zhong, C.B., Sun, N.J., Chi, R.A., 2018. Swelling of clay
minerals in ammonium leaching of weathered crust elution-deposited rare
earth ores. Rare Met. 37 (1), 72e78.