Article
Enhanced Stability of Scorodite in Oxic and Anoxic Systems
via Surface Coating with Hydroxyapatite and Fluorapatite
Sônia D. F. Rocha 1,*, Lydia Katsarou 2 and George P. Demopoulos 2,*
Citation: Rocha, S.D.F.; Katsarou, L.;
Demopoulos, G.P. Enhanced
Stability of Scorodite in Oxic and
Anoxic Systems via Surface Coating
with Hydroxyapatite and
Fluorapatite. Minerals 2022, 12, 1014.
https://doi.org/10.3390/min12081014
Academic Editors: Harshad Vijay
Kulkarni and Santanu Majumder
Received: 12 July 2022
Accepted: 10 August 2022
Published: 12 August 2022
Publisher’s Note: MDPI stays neu-
tral with regard to jurisdictional
claims in published maps and institu-
tional affiliations.
Copyright: © 2022 by the authors. Li-
censee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and con-
ditions of the Creative Commons At-
tribution (CC BY) license (https://cre-
ativecommons.org/licenses/by/4.0/).
Minerals 2022, 12, 1014. https://doi.org/10.3390/min12081014
1 Department of Mining Engineering, Universidade Federal de Minas Gerais (UFMG),
Belo Horizonte 31270-901, Brazil
2 Department of Mining & Materials Engineering, McGill University, Montreal, QC H3AOE9, Canada
* Correspondence: sdrocha@demin.ufmg.br (S.D.F.R.); george.demopoulos@mcgill.ca (G.P.D.)
Abstract: With the objective of enhancing the stability of scorodite, its encapsulation with hydroxy-
apatite (Ca5(PO4)3OH) (HAP) and fluorapatite (Ca5(PO4)3F) (FAP) surface coatings, the two most
stable of the calcium phosphates, inert to pH and redox potential variations, are presented in this
work. The experimental work includes: (1) determination of the metastable zone for HAP and FAP
precipitation, (2) the synthesis of crystalline scorodite under atmospheric conditions using hydro-
thermal scorodite seed and its characterization, (3) the coating of scorodite with hydroxyapatite and
fluorapatite with supersaturation-controlled heterogeneous crystallization, and (4) the long-term
stability of the encapsulated scorodite solids. Hydroxyapatite and fluorapatite were prepared with
homogeneous precipitation from a metastable solution to which reagents were added at a controlled
flow rate. Crystalline scorodite was produced with seeding precipitation and encapsulated with a
direct apatite (HAP or FAP) deposition that was controlled by adjusting the pH and reagent addi-
tion. The stability tests in oxic and anoxic environments over the pH range of 5–9 showed the release
of arsenic from the apatite-coated scorodite to be much lower than from naked scorodite, thereby
demonstrating that apatite-based encapsulation of hazardous materials is technically feasible and
merits further consideration for development into an arsenic stabilizing technology.
Keywords: arsenic wastes; scorodite; encapsulation; hydroxyapatite; fluorapatite; crystallization
1. Introduction
The harmful presence of arsenic in waters from both natural and anthropogenic ori-
gins is widely known [1]. Despite the number of studies aiming to remove As from con-
taminated waters, there are still difficulties regarding the low stability of solid arsenic
wastes, including the relatively insoluble crystalline scorodite compound (FeAsO4·2H2O)
whose stability depends on the pH and redox potential (Eh) of the surrounding aqueous
solution [2].
There have been increasingly strict environmental regulations [3] aimed at minimiz-
ing the concentrations of arsenic in mining and metallurgical industry wastewaters.
Worldwide, the limiting value for arsenic in wastewaters discharged into the environment
is 0.5 mg/L, and according to the World Health Organization [4] the level of arsenic in
drinking water should be limited to 0.01 mg/L. On the other hand, the leachability limit
for industrial arsenic wastes (TCLP) is set at 1 mg-As/L [5,6].
Depending on the As concentration in the solution, different approaches may be ap-
plied for its removal, including adsorption [7,8] (co-precipitation [8](Jia and Demopoulos
2005), precipitation of various metals (iron (II or III), copper, calcium and manganese),
arsenates [9,10], svabite [11,12] and arsenate-hydroxyapatite [13]). More recently, electro-
chemical methods have also been used [14,15].
The most widely employed method to immobilize As from mineral processing in-
dustrial effluents is iron (III) arsenate co-precipitation by concurrent lime addition [16].
www.mdpi.com/journal/minerals
Minerals 2022, 12, 1014 2 of 19

This process has been studied and optimized recently by De Klerk and co-workers [17,18],
but it is better suited for low As-concentration solutions as it requires an iron (III) to arse-
nic (V) molar ratio of ≥3 adding to the cost, not to mention the voluminous tailings gener-
ated, composed of poorly crystalline ferric arsenate and ferrihydrite with adsorbed arse-
nate mixed with gypsum [6,19] ). However, in the case of effluents, or arsenical wastes in
general, that are rich in arsenic, a better option would be to immobilize arsenic in the form
of scorodite [8], a crystalline ferric arsenate compound naturally occurring in nature [20].
Scorodite was successfully precipitated in a continuous system using industrial
wastewater from the gold industry [21] while Min and co-workers [22] precipitated it from
an alkaline liquor of leaching an anode lime rich within their research.
Scorodite has several advantages, such as low iron content since the iron-to-arsenic
ratio is 1:1; and it can be easily dewatered, in contrast to amorphous sludge formed by co-
precipitation. The product obtained is generally considered as satisfactorily stable for dis-
posal purposes, since it can pass the TCLP limit of [As] <1 mg/L after 20 h of extraction
period at pH 5 [5].
Conversely, scorodite undergoes incongruent dissolution at pH values over five, re-
leasing arsenic into the solution as it converts to ferrihydrite (FeOOH) (see Equation (1))
to progressively larger extents as the pH is elevated into the alkaline region. In other
words, its stability is strongly influenced by pH, meaning that for pH values in industrial
tailings ponds higher than seven, the dissolution of scorodite may release arsenic in the
surrounding water above the permissible levels.
FeAsO4·2H2O(s)  FeOOH(s) + H3AsO4 (aq) (1)
Solubility results from Bluteau and Demopoulos [2] show that at pH 7, the equilib-
rium concentration of arsenic is 5.8 mg/L for hydrothermally prepared crystalline scoro-
dite, which agrees with the value of 5.4 mg/L obtained by Paktunc and Bruggeman [23])
for nanocrystalline scorodite. At higher pH, arsenic concentration increases to unaccepta-
ble higher levels (e.g., >80 mg/L at pH 8), hence justifying the need to enhance the stability
of scorodite. Under anoxic conditions, at a redox potential in reference to hydrogen (Eh)
near or below 250 mV [24], scorodite undergoes reductive decomposition to Fe(II) and
As(III), according to Equation (2), leading again to a significant release of arsenic.
FeAsO4·2H2O (s) + 3H+ + 3e−  Fe2+ + HAsO32− (aq) + 3H2O (2)
Recently, Das and Mandal [25] found high As concentrations (from 28.9 to 143 mg/L)
in shallow aquifers (<50 m) with a reductive environment in West Bengal, India, as well
as in sediments. Reductive conditions (low Eh) may prevail in cases where the deposition
of hazardous solid wastes, as in the case of scorodite, is sub-aqueous with the presence of
soluble organic carbon or at depths of approximately 2 m below the ground in an anaero-
bic environment, where reactive metal sulfides may act as a reducing agent [16] . Then,
the encapsulation of scorodite with stable compounds may prevent contamination with
the release of arsenic into the environment, both in anoxic and oxic conditions.
The enhancement of the stability of scorodite using aluminum phosphate, as well as
aluminum hydroxy gels, to minimize arsenic release in alkaline (pH > 7) environments
and reduce potential has been evaluated [26–28]. Aluminum hydroxy gels prepared by
controlled hydrolysis of aluminum solutions with sodium hydroxide were mixed with
scorodite particles and left to age. Scorodite particles were encapsulated in an aluminum
oxy-hydroxide matrix, which resulted in a reduced arsenic release. A uniform coating of
scorodite particles with aluminum phosphate as an encapsulation layer was obtained, but
the long-term stability results showed that it was slowly dissolving over time, and there-
fore, after a certain period, the coating would not offer sufficient protection [28]. After
encapsulation, the final solids can be safely disposed of in appropriate industrial landfills
for hazardous waste, since they are not commercially used for scorodite in the volumes that
are generated.
Minerals 2022, 12, 1014 3 of 19

In this work, hydroxyapatite (HAP) (Ca5(PO4)3OH) and fluorapatite (FAP)

(Ca5(PO4)3F), known for their high stability among the calcium phosphates, were used for
the encapsulation of scorodite particles using direct crystallization of these phosphates on
the scorodite surface. The improvement of the nature of HAP coating and the possibility
of forming coatings of fluorapatite around the scorodite particles, taking advantage of the
enhanced stability (lower solubility) of fluorapatite compared to hydroxyapatite was eval-
uated. Aqueous precipitation of hydroxyapatite and fluorapatite was based on supersat-
uration control of solutions [29] by adjusting the concentration of the ions, pH, and tem-
perature of the system to be within the metastable zone. This metastable region is located
between the solubility line and a line representing the critical solute concentration below
which heterogeneous nucleation occurs, and growth is favored [29]. The effectiveness of
the process is evaluated with appropriate solid characterization and the release of arsenic
in oxic and anoxic waters.

2. Experimental Section
The experiments consisted of (i) scorodite synthesis (ii), evaluation of hydroxyapatite
(HAP) and fluorapatite (FAP) metastable zones (iii), encapsulation experiments with het-
erogeneous deposition of hydroxyapatite or fluorapatite under atmospheric conditions of
scorodite particles and (iv) stability evaluation of the naked and encapsulated scorodite. All
reagents used were of analytical grade, As2O5·xH2O, CaSO4·2H2O, HCl, Ca5(PO4)3OH, Ca5(PO4)3OH
e Fe2(SO4)3·xH2O (Sigma Aldrich, St. Louis, MO, USA), NaF (Anachemia, Lachine, QC, Canada),
NaOH, Na2SO3, H2SO4, CaCl2·2H2O and CaO (Fisher Scientific, Waltham, MA, USA).

2.1. Preparation and Characterization of Scorodite

Scorodite seeds produced hydrothermally were used to precipitate scorodite under
atmospheric conditions, as described in previous work [28]. The preparation of scorodite
consisted of mixing solutions of arsenic pentoxide of 40 g/L As and ferric sulfate with a
molar ratio Fe/As of 1. The seeds were introduced to the solution and the temperature was
kept stable at 85 °C, for 2 h. Further, the kinetics of the precipitation were sped up with
the increase in temperature to 95 °C and the system was kept under stirring for 9 h. At the
end of the experiment, the solution was left to cool down, filtered, washed, and dried.
Both scorodite solids and seeds were characterized by X-ray diffractometry-XRD (Philips
PW 1710 X-Ray Diffractometer) (Eindhoven, The Netherlands) with a copper target (Cu
Kα1 radiation, λ = 1.5405 Å) and TGA (Thermogravimetric analysis) by Perkin-Elmer ther-
mogravimetric analyzer model TA Instruments Q500 TGA (Waltham, MA, USA). The
chemical groups of the solids were obtained by ATR-IR (attenuated reflectance infrared)
spectra with a Perkin Elmer (Waltham, MA, USA) (Spectrum BX model) Fourier Trans-
form Infrared (FTIR) spectrometer spectrum BX-model. The particle size distribution was
obtained using Horiba LA-920 Laser (Kyoto, Japan) scattering analyzer and solids mor-
phology was observed at SEM (scanning electron microscope Jeol JSM-840A) (Glen Ellyn,
IL, USA). In addition, secondary electron microscopy analysis and elemental mapping
were also obtained using a variable pressure scanning electron microscope (SEM-type Hi-
tachi S-3000N) (Schaumburg, IL, USA). A Micromeritics TriStar 3000 was used to measure
the BET surface area of the scorodite particles.
Minerals 2022, 12, 1014 4 of 19

2.2. HAP and FAP Precipitation and Metastable Width Zone Determination
A series of homogeneous precipitation experiments of hydroxyapatite and fluorap-
atite were performed, so that the metastable zones of the precipitation reactions could be
determined [27,29] For these experiments, solutions with different initial Ca and P con-
centrations were prepared by dissolving CaCl2·2H2O and anhydrous NaH2PO4 at a molar
ratio of Ca/P = 1.67 and subsequently carefully neutralized with sodium hydroxide. The
pH was increased gradually at a rate of 0.1 pH points per 5 min using 0.01 N sodium
hydroxide solution. As soon as the solution became cloudy, the pH increase was stopped,
and the solution was left to equilibrate for 24 h. The diagrams resulting from these exper-
iments consist of two curves bounding the metastable region; the upper one for the pH
and concentration at which precipitation (cloud formation) was first observed, and the
lower one for the pH and concentration at pseudo-equilibrium (end of 24-h equilibration
period). The experiments were carried out at 25 °C and 40 °C. The same procedure that
was followed for hydroxyapatite was also adopted for fluorapatite; the only difference
being that F− was also present in the phosphate solution (added as NaF) at molar ratio
Ca/F = 5.

2.3. Encapsulation Experiments

Scorodite encapsulation was carried out in the metastable region for the Ca-P-H2O
(HAP precipitation) and Ca-F-P-H2O (FAP precipitation) systems, for Ca/P = 1.67 and Ca/F
= 5, at 22 °C and at a stirring rate of 500 rpm. The process involved separate nucleation
and growth steps, which were used in distinct combinations of conditions.
To prepare the surface of the scorodite particles for encapsulation, they were sub-
jected to a pre-equilibration called the conditioning treatment (C) with (i) 5 g/L scorodite
in aqueous solution of pH 7.6 (adjusted with NaOH), for 15–30 min under mild stirring
on an orbital shaker or (ii) 15 g/L scorodite were conditioned in a solution containing 10
mmol/L of CaCl2. Solids were separated with vacuum filtration in 22 µm membranes.
The heterogeneous nucleation of apatite coating on scorodite particles (N) was in-
duced by contacting the 5.0 g/L of scorodite with a metastable solution for specific times.
Nucleation of HAP was carried out at P: 0.9 mmol/L; Ca: 1.5 mmol/L (Ca/P: 1.67); pH: 7.6
to prevent homogeneous nucleation of calcium phosphates as indicated by the metastable
region. Growth of 5.0 g/L of scorodite was carried out with 60 mmol/L P or 100 mmol/L
Ca solutions. The stirring rate was varied from 85 to 350 rpm and the number and duration
of nucleation cycles varied from 1 to 5 and from 1 to 24 or 48 h, respectively. Experiments
were conducted at two temperatures: 22 °C and 40 °C. Between stages, the solids were
waited to settle down; the solution was drained, and the subsequent stage was carried
out.
The growth step (G) was carried out in two distinct modes (i) by adding the scorodite
solids to the calcium phosphate metastable solution and after 30 min of contact, the addi-
tion of the two 60 mmol/L P or 100 mmol/L Ca at pre-determined fixed flow rates or (ii)
scorodite particles were introduced to the reactor containing the calcium phosphate met-
astable solution, and after 30 min the Ca and P solutions were added, with flow rates
regulated by the pH that was controlled to prevent overshooting the set value that could
cause homogeneous precipitation. The concentrations of the feed solutions for the exper-
iments with the flow rate regulated by pH were calculated according to the equations
given in the work of Wu and Nancollas [30] as 10.8 mmol/L P and 18 mmol/L NaOH in
one solution and 18 mmol/L Ca and 270 mmol/L NaCl in the other solution.
The fluorapatite encapsulation experiments were carried out with 3.5 mmol/L F
added to the phosphate solution. The default experimental condition for FAP deposition
was pH 7.4, supported by the metastable region obtained from Section 2.2, a temperature
of 37 °C and a stirring speed of 500 rpm.
The encapsulation experiments consisted of:
Minerals 2022, 12, 1014 5 of 19

(i) Encapsulation A (ENCH-A): Scorodite in 9 nucleation steps followed by one step of

growth carried out with flow rates of 20 mL/h of 60 mmol/L P plus 100 mmol/L Ca at
22 °C, pH 7.4 for 7 h.
(ii) Encapsulation B (ENCH-B): Scorodite in 9 nucleation steps followed by growth ac-
cording to the procedure suggested by Wu and Nancollas [30] at 37 °C pH 7.4; in this
case, the addition of constituent elements is not performed at fixed rates but accord-
ing to pH variation.
(iii) Encapsulation C (ENCH-C): Previous conditioning of scorodite with 4.25 M CaCl2
solution at pH 6.0 for 15 h, before the procedure of Wu and Nancollas [30] at 37 °C
pH 7.4. Here, a stronger CaCl2 solution was adopted for conditioning to populate the
surface with Ca ions hence facilitating the subsequent nucleation-growth steps (not
shown in this paper).
(iv) Encapsulation D (ENCH-D): Scorodite in two stages of nucleation (N) the first one at
pH 6.0–6.5, considering the metastable region of FAP and the second at pH 7.0, and
two steps of growth.
(v) Encapsulation E (ENCH-E): Scorodite was previously conditioned in calcium chlo-
ride solution and subjected directly to one step of deposition-growth.

2.4. Stability Evaluation

Evaluation of scorodite leachability under oxic or anoxic conditions at pH 8 and
sometimes pH 7 and 9 was monitored over many days at room temperature (22 °C). The
anoxic solutions (Eh = 150 or 200 mV) were monitored with a Cole-Parmer® ORP platinum
combination electrode (Ag/AgCl), set up to read directly the Eh, considering the unit con-
version factor of +194 mV and a specified probe accuracy of ±40 mV. Additionally, two
control stability tests of a physical mixture of scorodite and 15% hydroxyapatite were per-
formed at pH 8 and Eh = 150 mV to verify if the presence of the hydroxyapatite powder in
the suspension would affect the arsenic release from the scorodite. The stability tests were
conducted in 250 mL Erlenmeyer flasks held in an orbital shaker using a 40:1 liquid-to-
solid ratio. Ca(OH)2 saturated deionized water slurry (14.76 g in 500 mL) and a 5% HCl
solution were used to adjust pH, while a 1.4 mol/L Na300O3 solution was used to adjust the
Eh to the required anoxic ORP.
For some tests, gypsum was added (4 g CaSO4·2H2O4 in 200 mL) to evaluate possible
interaction with the apatite-coated scorodite, such as the one reported by previous work
[31] The pH was adjusted regularly within ±0.2 units of the target value and the Eh was
measured and adjusted, if necessary, to be ±40 mV of the target value, 150 mV for HAP
and 200 mV for FAP. The samples taken from the stability tests were filtered with 0.22 μm
pore-size syringe filters and diluted with acidified HNO3 (~5 wt.%) in deionized water
and chemically analyzed by inductively coupled plasma atomic emission spectrophotom-
etry (ICP-AES) for As, Fe, Ca and P concentrations.
In the case of F, Ion Chromatography (IC) was used. Ascorbic acid UV colorimetric
method for P with a Perkin Elmer Lambda 20 UV-Vis Spectrometer (Waltham, MA, USA)
was used to validate the ICP-AES results or when the on-the-spot analysis of the phos-
phorus levels was required to control supersaturation and avoid homogeneous precipita-
tion during the encapsulation tests. The experimental strategy is graphically described in
Figure 1.
Minerals 2022, 12, 1014 6 of 19

Figure 1. Experimental methodology for scorodite encapsulation and arsenic stability evaluation.

3. Results and Discussion

3.1. Scorodite Preparation
The precipitated scorodite particles were highly crystalline, as indicated by the nar-
row peaks in the XRD pattern shown in Figure 2a. The FTIR spectroscopy (Figure 2b) was
also as expected for scorodite based on previous work [32] The thermo-gravimetric anal-
ysis yielded 15.6% of weight loss between 100 °C and 200 °C which is equal to the theo-
retical value. The BET surface area was 0.755 m2/g and the average particle size was 19.8
μm.

100

95 3517 1060,
Atmospheric scorodite OH-H2O 1588 1090
2971 H2O SO4
OH-H2O
90
Intensity (%)

Intensity

85

80
scorodite ref#: 00-019-0603

75 785
AsO4

10 20 30 40 50 60 4000 3500 3000 2500 2000 1500 1000

2θ(°) Wavenumber (cm-1)

(a) (b)
Figure 2. XRD (a) and FTIR (b) spectra of the atmospherically precipitated scorodite.

3.2. HAP and FAP Metastable Width Zone Determination

Hydroxyapatite (HAP) is more soluble than fluorapatite (FAP). There is some varia-
tion in reported Ksp values due to the use of various methodologies and conditions (Wei
et al. 2013). According to [33] Ksp values calculated by using PHREEQC for HAP varied
from 10−53.02 to 10−53.51 and for FAP values ranged from 10−55.18 to 10−56.13 at 25 °C and pH 7.8
[32]. Using distinct initial pHs, [34] observed a reduction in solubility in acidic media.
They obtained mean Ksp values for HAP of 10−57.72 (10−57.39~10−58.05) and for FAP of 10−59.08
(10−58.65~10−59.75) at 25 °C at initial pH 2.
In the present work, thermo-dynamic calculations were conducted using the OLI Sys-
tems electrolyte simulation software, analyzer version 3.0 (Parsippany, NJ, USA), and the
Minerals 2022, 12, 1014 7 of 19

respective solubility products were calculated as well. The values obtained are within the
range observed in the literature. On the pre-supposition that these compounds have very
low solubilities, the activity coefficients of the ions in an aqueous solution (pH = 7.0) were
assumed to be very close to one, giving the Ksp for HAP and FAP as per Equation (3) and
Equation (4), respectively.
Ksp, 25 °C (HAP) = [Ca2+]5 [PO43−]3[OH−] = 10−56.55 (3)
Ksp, 25 °C (FAP) = [Ca2+]5 [PO43−]3[F−] = 10−59.54 (4)
Additionally, the knowledge of the metastable zone width of HAP and FAP was essential
to designing the precipitation experiments to favor heterogeneous nucleation instead of ho-
mogeneous nucleation. The metastable zones of the apatite precipitation compounds defined
in terms of phosphorus concentration (concentration vs. pH) are presented in Figure 3. Based
on these curves, the direct deposition of HAP/FAP on scorodite was attempted at either
pH 7.6 with a starting P concentration of 0.9 mmol/L but not exceeding 1.2 mmol/L during
the experiments, or at pH 7.0, with a starting P concentration of 2 mmol/L but not exceed-
ing 2.5 mmol/L during the experiments. As depicted, the zones for HAP and FAP are sim-
ilar, however, fluorapatite tends to precipitate in advance at a lower pH value for the same
phosphorus concentration. Therefore, the conditions for FAP deposition experiments
were kept as those used for HAP using three feed solutions, in this case, namely NaH2PO4
30 mmol/L, CaCl2 50 mmol/L and NaF 10 mmol/L.
The nucleation step consisted of immersion of the scorodite particles into the meta-
stable solution for several hours to induce the apatite nucleation on the foreign surface of
the scorodite. As the induction period for such nuclei formations proved rather long, it
was decided to immerse the same substrate in more than one fresh metastable solution,
i.e., to try multiple nucleation steps with repeated contacts. In this way, the creation of an
initial nucleation layer was hoped to form on the surface of the scorodite particles, making
them amenable to encapsulation by the subsequent growth stage. The growth stage con-
sisted of a semi-batch experiment where the apatite surface-nucleated scorodite particles
were transferred to a metastable solution in which the constituent elements (Ca, P plus F
in the case of FAP) feed solutions were added at a pre-determined flow rate. Note that
prior to starting the addition of the feed solutions into the crystallization reactor, the solids
were allowed 30 min for additional conditioning.

7 7
6.5 6.5
6 (a) 6 (b)
P Concentration (mmol/L)
P Concentration (mmol/L)

5.5 5.5
5 5
4.5 4.5
4 4
3.5 3.5
3 3
2.5 2.5
2 2
1.5 1.5
1 1
0.5 0.5
0 0
5.5 6.5 7.5 8.5 5.5 6.5 7.5 8.5 9.5

pH
pH
Minerals 2022, 12, 1014 8 of 19

7
6.5
6 (c)

P Concnetration (mmol/L)
5.5
5
4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
6 7 8 9
pH
Figure 3. Metastable zones for the CaCl2-NaH2PO4-NaOH system at (a) (22 ± 1) °C and (b) (40 ± 1)
°C and (c) CaCl2-NaH2PO4-NaF system at (22 ± 1) °C.

3.3. Encapsulation
3.3.1. Encapsulation of Scorodite with Hydroxyapatite
With the aim of preventing homogeneous nucleation, the flow rate of the reagents
was set to 6 mL/h during the first 24 h and then increased to 20 mL/h (aleatory value) in
the subsequent five steps. However, using this flow rate, the critical concentration of P of
1.2 mmol/L (see metastable zones in Figure 3) was exceeded, causing homogeneous nu-
cleation and precipitation away from the scorodite particle surfaces. As a result, it was
decided to abandon this type of nucleation procedure in favor of multiple contacts to the
scorodite particles with fresh calcium phosphate solution.
Scorodite particles were brought into contact with a series of five calcium phosphate
metastable solutions, for one hour at a time. A very small decrease in the concentration of
P and Ca was noticed during these steps, however, the analysis of SEM images indicated
that some precipitation had happened away from the scorodite particle surfaces, even at
a longer time of 48 h. The effects of stirring speed and temperature were evaluated. During
these tests, it was noticed that phosphorus and calcium were removed from the solution
as soon as the scorodite was introduced with the amount removed, increasing with in-
creasing temperature and decreasing stirring speed, as seen in Figure 4.

Ca P

1.5
Concnetration (mmol/L)

22 oC
1.3 350 rpm

1.1

0.9

0.7

0.5
0 10 20 30 40 50
Time (h)

(a)
Minerals 2022, 12, 1014 9 of 19

Ca P
1.4
1.3
40 oC
1.2

Concnentration (mmol/L)
350 rpm
1.1
1
0.9
0.8
0.7
0.6
0.5
0 10 20 30 40 50
Time (h)

(b)

Ca P

1.4
40 oC
Concentration (mmol/L)

1.3
850 rpm
1.2
1.1
1
0.9
0.8
0.7
0.6
0.5
0 10 20 30 40 50

Time (h)
(c)
Figure 4. P and Ca concentrations as a function of time during three nucleation experiments at (a)
22 °C and 350 rpm, (b) 40 °C and 350 rpm and (c) 40 °C and 850 rpm.

Low agitation speed and higher temperature (higher solubility, therefore lower su-
persaturation) stimulated the heterogeneous precipitation of calcium phosphate on the
surface of scorodite and these conditions were adopted for the rest of the work. It must be
noted, however, that when the solids were examined by SEM it was not possible to ob-
serve any surface layer nor any homogeneously precipitated particles. The latter, i.e., the
absence of dispersed HAP particles was taken as evidence of successful heterogeneous
nucleation although such surface layer could not be detected due to a very low amount of
calcium phosphate coating.
In subsequent experiments, multiple nucleation steps (9) were used to obtain a better
coverage of the scorodite particles by HAP, hence facilitating the subsequent growth
stage. At this time, the operation point was changed to a higher supersaturation, 2 mmol/L
P, 3.34 mmol/L Ca and pH 7.0, but still operating within the metastable zone, as shown in
Figure 4. Therefore, to complete the HAP deposition, three approaches as described in
Section 2.3 for growth were adopted: ENCH-A, ENCH-B and ENCH-C.
The SEM images of the resulting scorodite@HAP solids obtained with the encapsu-
lation A and encapsulation B methods are presented in Figure 5. From ENCH A, the scor-
odite particles seem to be only partially covered by hydroxyapatite, while still a large
amount of hydroxyapatite is seen to have formed away from the scorodite surface due to
homogeneous precipitation. Additionally, there were small hydroxyapatite particles at-
tached to the bigger scorodite particles. FTIR analysis of the solids (not shown in this
Minerals 2022, 12, 1014 10 of 19

paper) from the encapsulation A approach identified the characteristic features of hydrox-
yapatite and scorodite but could not distinguish between homogeneously and heteroge-
neously nucleated HAP. Particle size analysis was not conducted after encapsulation,
hence the layer deposited was very narrow.

(a)

(b)
Figure 5. SEM cross-section images of resulting scorodite@HAP solids from (a) ENCH-A 60 mmol/L
P and 100 mmol/L Ca, 9 nucleation steps. Growth in 1 step of 20 mL/h, 22 °C for 7 h and (b) 9
nucleation steps and growth at 37 °C and pH 7.4 for 6 h.

Encapsulation method B (ENCH-B) allowed for a constant composition environment

to be maintained, i.e., it enabled a better control of supersaturation, and as a consequence,
there was an improvement in the formation of scorodite@HAP solids. The SEM cross-sec-
tion images of the encapsulated material revealed the majority of the scorodite particles
to have been partially covered with hydroxyapatite; in addition, there was a significant
occurrence of agglomerates of hydroxyapatite and scorodite sub-particles.
In the subsequent approach of encapsulation C, it was hypothesized that by condi-
tioning the scorodite particles in a concentrated CaCl2 solution (4.25 mol/L), the particle
surface/inner side of the electrical double layer will be enriched with Ca2+ hence, creating
a favorable localized environment for phosphate anions to approach (during the subse-
quent deposition test) and form in situ HAP nuclei. The affinity of Ca2+ ions to the surface
of scorodite is supported further by the isoelectric point (IEP) of scorodite, determined by
the zeta-potential measurements to be at pH = 3.9. That means the scorodite surface is
negatively charged, which favors electrostatic attraction of Ca2+ at precipitation pH ~ 7.5.
The conditioning step involved equilibration for 15 h of 15 g of wet scorodite in 1 L
of 4.25 M CaCl2 solution. Indeed, the calcium concentration dropped to 3.77 M Ca at the
end of this conditioning step, apparently due to adsorption or surface precipitation of a
calcium arsenate as described in the literature [10,22] The subsequent deposition (growth)
step (32 h) was found to have a short induction time in comparison to the deposition
Minerals 2022, 12, 1014 11 of 19

growth on naked scorodite, which had not been previously conditioned with a CaCl2 so-
lution other than immersing it in pH 7.6 water. After 32 h, the feed solutions were com-
pletely consumed. This means that conditioning with the calcium solution had effectively
prepared the particle surface for extensive heterogeneous nucleation and growth of hy-
droxyapatite to take place, thus, favoring the formation of well-encapsulated scoro-
dite@HAP material as confirmed by SEM examination, as shown by SEM in Figure 6.
Clearly, heterogeneous deposition of HAP on scorodite took place. Elemental X-ray map-
ping of one of the cross-sections shows that the layer covering the scorodite particle is
indeed a calcium phosphate compound. Additionally, the images reveal that the layer has
not grown uniformly over the whole particle surface, and further studies to optimize the
growth of the HAP coating are required.

Figure 6. SEM images of resulting scorodite@HAP solids from encapsulation method C (ENCH-C)
(top); and backscattered electron image of a partially coated scorodite particle’s cross-section along
its elemental maps revealing its coating with HAP.

3.3.2. Encapsulation of Scorodite with Fluorapatite

Having determined in the previous series of tests that conditioning of the scorodite
particles in CaCl2 solution is beneficial to subsequent heterogeneous deposition, the same
approach was adopted to evaluate fluorapatite as a coating material. After scorodite con-
ditioning in calcium chloride solution, two routes were investigated for fluorapatite pre-
cipitation: two stages of nucleation (N), the first one at pH 6.0–6.5, considering the meta-
stable region of FAP in Figure 4, and the second at pH 7.0, as described in Experimental
Section, and two steps of growth labeled as encapsulation D (ENCH-D). The decrease in
the concentrations of Ca, P and F during the two nucleation steps of ENCH-D signalized
that nucleation of FAP had taken place.
In the other route, nucleation was bypassed, and scorodite that was previously con-
ditioned in calcium chloride solution was subjected directly to one step of deposition-
growth; this strategy is specified as “Encapsulation E”. The successful coating of scorodite
particles with FAP was evaluated with SEM with images presented in Figure 7. In this
image, the FAP-coated scorodite particles after the growth step following conditioning
with calcium chloride solution are depicted. The darker layers around some particles
Minerals 2022, 12, 1014 12 of 19

indicate coating formation, substantiated by the backscattered electron image and the cor-
responding elemental maps revealing phosphorus and calcium rims, confirming a core-
shell type scorodite@FAP formation. The presence of fluorine was not detected due to
limitations of the technique regarding light elements. In the meantime, due to small
amounts of FAP coating, XRD and IR spectra could not detect the presence of FAP. The
employment of the encapsulation E method that involved only conditioning in CaCl2 so-
lution and growth-deposition of FAP without an in-between nucleation stage proved suc-
cessful as it could be validated with the SEM images, which revealed a well-developed
phosphate coating on scorodite particles, thus, proving the effectiveness of calcium chlo-
ride conditioning.

Figure 7. Backscattered electron image and elemental mapping of scorodite@FAP particles pro-
duced with the ENCH-E.

3.4. Stability in Oxic and Anoxic Environments

The variables pH and Eh were measured and adjusted regularly to the set point dur-
ing the stability tests. However, the variations in Eh were not easy to control. The value
for anoxic experiments with HAP coating is 150 ± 40 mV and for FAP is 200 ± 40 mV. As
they are related variables, a change in pH modifies Eh and vice-versa. In industrial prac-
tice, the pH is usually adjusted with time, and since sulfate ions are common in the
wastewater, the presence of gypsum in the system must be considered. Due to this fact,
the release of arsenic in the presence of gypsum was measured.

3.4.1. Stability of HAP-Encapsulated Scorodite

The release of arsenic in the oxic condition, as shown in Figure 8, was reduced signif-
icantly upon coating with HAP (ENCH-A) when compared to that of the naked scorodite.
It is clear, therefore, that the surface deposition of a hydroxyapatite layer has a protective
effect on scorodite, especially in the alkaline (pH > 7) region, where scorodite is the least
Minerals 2022, 12, 1014 13 of 19

stable. Thus, while at pH 9 the naked scorodite sample released 0.29 mmol/L (22 mg/L) of
As, the coated material released only 0.014 mmol/L (1.1 mg/L) of As. This value is slightly
lower in the presence of gypsum, giving a value of 0.011 mmol/L (0.8 mg/L) of As after 40
days of equilibration, apparently reflecting the common ion effect on the solubility of
HAP. In addition to arsenic, the release of P was monitored, and it varied from 0.0098
mmol/L (0.28 mg/L) at pH 9 to 0.21 mmol/L (6.5 mg/L) at pH 7. This was slightly reduced
in the presence of gypsum: 0.21 mmol/L (6.5 mg/L) vs. 0.076 mmol/L (2.3 mg/L) at pH 7.
The Fe concentration was found to be very low, below the detection limit (0.1 mg/L) for
all samples, which was expected, since at these pH values iron precipitates as ferrihydrite.

0.35
0.3 pH 7
Concentration (mmol/L)

0.25
0.2
0.15
0.1
0.05
0
0 10 20 30 40 50 60 70 80
Time (days)
Scorodite Scorodite ENCH-A Scorodite ENCH-A +Gypsum

(a)

0.35
pH 8
Concentration (mmol/L)

0.3
0.25
0.2
0.15
0.1
0.05
0
0 10 20 30 40 50 60 70 80
Time (days)
Scorodite Scorodite ENCH-A Scorodite ENCH-A +Gypsum
(b)
Minerals 2022, 12, 1014 14 of 19

0.35
0.3
pH 9
Concentration (mmol/L) 0.25
0.2
0.15
0.1
0.05
0
0 10 20 30 40 50 60 70 80
Time (days)
Scorodite Scorodite ENCH-A Scorodite ENCH-A +Gypsum

(c)
Figure 8. As release in oxic stability tests at (a) pH 7, (b) pH 8 and (c) pH 9 from naked scorodite
and scorodite coated with HAP according to encapsulation method A in gypsum-free (ENCH-A)
and gypsum-saturated water (ENCH A+Gypsum) at 22 °C.

The results in anoxic conditions are plotted in Figure 9. After 20 days, in general, the
release levels were stabilized, signaling near pseudo-equilibrium attainment. In an anoxic
environment of 150 ± 40 mV, the naked scorodite sample was found to release 2.3 mmol/L
As. Encapsulation A and B produced a scorodite@HAP that releases 60% less arsenic than
the naked scorodite. These procedures were slightly better protected than ENCH-C, since
the arsenic release at pH 8 was ~0.9 mmol/L for ENCH-A and ENCH-B versus 1.2 mmol/L
As for ENCH-C. At pH 9.0, ENCH-A yielded a 30% decrease in As release, from ~1.3
mmol/L (110 mg/L) to 0.395 mmol/L (30 mg/L).
However, this level of protection is not considered adequate given that the environ-
mentally acceptable level of the typical leachability tests, such as EPA’s TCLP, is required
not to exceed 5 mg/L or, in other jurisdictions, 1.0 mg/L As. The underlying cause of the
significantly different responses of the HAP-coated scorodite to the oxic and anoxic envi-
ronments is not clear. It may be due to the incomplete growth of a non-porous continuous
layer of HAP on the surface of all scorodite particles, allowing for the sulphite-reducing
species to reach the surface and initiate degradation of part of the scorodite via the reduc-
tion in Fe(III) to Fe(II). This hypothesis seems to be supported by the relatively higher
release of arsenic from the physical mixture of scorodite with hydroxyapatite (sample
“Scoro+HAP ref”) vis-à-vis the coated samples.
Additionally, some degree of solubilization of the deposited HAP was observed, de-
pending on the kind of deposition method used. The release of phosphorus was reduced
following the order ENCH-A > ENCH-B > ENCH-C. This again points to the beneficial
effect of the calcium chloride conditioning step in facilitating the deposition of a robust
HAP coating layer.
Minerals 2022, 12, 1014 15 of 19

2.5

(a)
2.0
As Concnetration (mmol/L)

1.5

1.0

0.5

0.0
0 10 20 30 40 50
Time (days)
SCOr ENCH-B ENCH-C ENCH A+Gypsum ENCH-A SCOR+HAP

5.0
(b)
4.0
Concentration (mmol/L)

3.0

2.0

1.0

0.0
0 10 20 30 40 50

Time (days)

Ca-ENCH-A Ca-ENCH-A +Gypsum Ca-ENCH- B Ca-ENCH-C

P-ENCH-A P-ENCH-A +Gypsum P-ENCH-B P-ENCH-C

Figure 9. Arsenic release (a) and Ca and P (b) under anoxic conditions (pH 8; 150 mV) from various
HAP-coated and naked scorodite materials, gypsum-free and gypsum-containing waters.

3.4.2. Stability of FAP-Encapsulated Scorodite

A new batch of scorodite was created for FAP encapsulation tests, for this reason, the
stability results were compared with the new sample, which had essentially similar re-
lease characteristics as the previous one. Table 1 summarizes the stability data for FAP-
encapsulated scorodite and its comparison to that of naked scorodite. It is important to
highlight that scorodite encapsulated with FAP according to the encapsulation method E
has not been effective in protecting the scorodite, despite the layer of calcium phosphate
being well evidenced (figures not shown in this paper). It is possible that, due to fast pre-
cipitation, the deposited layer was very porous due to poor heterogeneous deposition and
inadequate protective FAP layer formation. In contrast, the encapsulation method D,
Minerals 2022, 12, 1014 16 of 19

which also involved preconditioning of scorodite in a concentrated calcium chloride so-

lution, proved effective as it enabled the formation of a good FAP coating.

Table 1. Summary of released (mmol/L and in mg/L) data after 6 and 10 days in oxic (O) and anoxic
(A, 200 ± 40 mV) environment at 22 °C from naked scorodite and scorodite@FAP at different pHs.

pH 7 pH 9
Oxic Anoxic Oxic Anoxic
Naked Scorodite
6 days (mmol/L) 0.094 0.291 0.210 1.009
6 days (mg/L) 7.04 21.80 15.7 75.59
10 days (mg/L) 8.99 23.44 nd nd
20 days (mg/L) 10.24 nd 20.22 n.d.
ENCH-D-Sco@FAP
6 days (mmol/L) 0.057 0.177 0.057 0.138
6 days (mg/L) 3.99 13.28 4.26 10.38
10 days (mg/L) 4.24 16.74 5.10 11.22
20 days (mg/L) 3.21 20.66 6.67 12.83

As can be verified with the data in Table 1, the FAP-encapsulated scorodite (obtained
with the encapsulation D method) was released after 20 days, under oxic conditions and
pH 9.0, with three times less arsenic, 0.089 mmol/L (6.67 mg/L) than the unprotected scor-
odite, 0.27 mmol/L (20 mg/L), and seven times less under an anoxic condition in 6 days
(76 mg/L versus 10 mg/L). Thus, it is deduced that the fluorapatite layer effectively coated
the surface of scorodite, and the observation is consistent with the elemental mapping
shown in Figure 9.
The respective numbers after 6 days of testing in an oxic system at pH 7.0 were 0.094
mmol/L (7 mg/L) As for naked scorodite and 0.076 mmol/L (5.7 mg/L) As for the HAP
encapsulated material, and a similar result of 0.053 mmol/L (4.0 mg/L) for scorodite@FAP.
By comparison, in an oxic system at pH 9.0, the HAP-coated scorodite yielded 1.1 mg/L
As, i.e., lower than that of the FAP-coated material (4.3 mg/L), apparently reflecting better
continuous growth of the HAP layer. On the other hand, under an anoxic condition at pH
9.0, the concentration of released arsenic for the FAP-encapsulated materials is only 14%
(0.14 mmol/L) of that of naked scorodite (1.0 mmol/L), confirming once again the effec-
tiveness of the FAP layer. The corresponding value for the HAP-coated material was sig-
nificantly higher (1.5 mmol/L). The origin of this discrepancy may be attributed more to
the reducing Eh (150 vs. 200 mV), in which the stability was carried out for the HAP-coated
scorodite.
In summary, both HAP and FAP materials bring a significant reduction in arsenic
release when deposited on scorodite, especially under the oxic condition. The results at
pH 9/oxic conditions with ≤5 mg/L As release (only ~1 mg/L for HAP vs. ~5 mg/L for FAP)
vis-à-vis that of a value >15 mg/L for unprotected scorodite clearly demonstrate the en-
capsulation potential of these systems. In terms of anoxic condition stability, the FAP sys-
tem looks more promising than the HAP system. Further work to optimize the coating on
one hand and evaluate other reducing agents—both abiotic and biotic—should be pur-
sued, to acquire further insight into the mechanism and build a totally robust encapsula-
tion system.

4. Conclusions
The encapsulation of scorodite via direct precipitation of apatite (hydroxyapatite-
HAP and fluorapatite-FAP) coatings and the stability of the products were studied under
oxic and anoxic environments. Encapsulation experiments of scorodite were conducted
by testing different combinations of procedures to enable the deposition of HAP/FAP on
Minerals 2022, 12, 1014 17 of 19

the scorodite particle surface via the control of supersaturation, and thus promote the for-
mation of a protective coating layer. Heterogeneous nucleation of calcium phosphates
proved to be difficult. After testing various procedures, prior conditioning of the scorodite
substrate in a calcium solution created favorable nucleation conditions, both for HAP and
FAP growth. Low agitation (500 rpm) and high temperature (37 °C) also proved beneficial,
as did the adaptation of the constant composition procedure of Wu and Nancollas (1997)
for the deposition of hydroxyapatite on titanium dioxide particles to the encapsulation of
scorodite. The coating layers formed on the particles were not as thick and continuous as
desired, an issue that should be addressed in future research. The long-term stability of
the encapsulated solids, as well as the scorodite alone and a simple physical mixture with
hydroxyapatite as controls, were tested, and the results clearly demonstrated that, in prin-
ciple, protection of scorodite via coating with hydroxyapatite/fluorapatite surface layers
is possible.
In all cases, the solids after the encapsulation experiments behaved much better than
the scorodite control sample, either under oxic or under anoxic conditions in the alkaline
region. By far the best results were obtained with the HAP-coated system under oxic con-
ditions, yielding < 1 mg/L As release after 20 days at pH 9, compared to 6.6 mg/L for the
FAP-coated material and 20 mg/L for the unprotected scorodite. In the meantime, the
FAP-coated material was found to be more stable than the HAP-coated scorodite when in
a reducing environment adjusted with sulfites, but further work with this system is re-
quired. Some of this work may involve the evaluation of biotic reducing agents that better
simulate anoxic conditions in disposed waste sites. Finally, another positive feature of the
tested encapsulation systems is the fact that the coatings released very low P levels, only
0.2–0.3 mg/L for both HAP and FAP; this level decreased even further in the presence of
gypsum due to the common-ion effect.

Author Contributions: Conceptualization, S.D.F.R., G.P.D. and L.K.; Data curation, L.K.; Formal
analysis, S.D.F.R., G.P.D. and L.K.; Funding acquisition, S.D.F.R. and G.P.D.; Investigation, S.D.F.R.
and L.K.; Methodology, S.D.F.R. and L.K.; Project administration, G.P.D.; Supervision, G.P.D.; Val-
idation, S.D.F.R., G.P.D. and L.K.; Writing—original draft, S.D.F.R. and L.K.; Writing—review and
editing, S.D.F.R. and G.P.D. All authors have read and agreed to the published version of the man-
uscript.
Funding: This research was funded by the Natural Sciences and Engineering Research Council of
Canada (NSERC) and the CNPq (process number 200295/2009-8).
Acknowledgments: The authors are grateful to the Brazilian agency CNPq (process number
200295/2009-8) and to the Natural Sciences and Engineering Research Council of Canada (NSERC)
and Teck Metals company for funding through a collaborative research R&D grant.
Conflicts of Interest: The corresponding authors declare that there is no conflict of interest.

References
1. Smedley, P.L.; Kinniburgh, D.G. A review of the source, behaviour and distribution of arsenic in natural waters. Appl. Geochem.
2002, 17, 517–568. https://doi.org/10.1016/s0883-2927(02)00018-5.
2. Bluteau, M.-C.; Demopoulos, G. The incongruent dissolution of scorodite—Solubility, kinetics and mechanism. Hydrometallurgy
2007, 87, 163–177. https://doi.org/10.1016/j.hydromet.2007.03.003.
3. Mandal, B.K.; Suzuki, K.T. Arsenic round the world: A review. Talanta 2002, 58, 201–235. https://doi.org/10.1016/S0039-
9140(02)00268-0.
4. Herschy, R.W.; Fairbridge, R.W. Water quality for drinking: Who guidelines. Springer Ref. 2011. https://doi. org/10.1007/spring-
erreference_30502.
5. Le Berre, J.F.; Gauvin, R.; Demopoulos, G.P. Characterization of poorly-crystalline ferric arsenate precipitated from equimolar
Fe(III)-As(V) solutions in the pH range 2 to 8. Metall. Mater. Trans. B Process Metall. Mater. Process. Sci. 2007, 38, 751–762.
https://doi.org/10.1007/s11663-007-9081-y
6. Nazari, A.M.; Radzinski, R.; Ghahreman, A. Review of arsenic metallurgy: Treatment of arsenical minerals and the immobili-
zation of arsenic. Hydrometallurgy 2017, 174, 258–281. https://doi.org/10.1016/j.hydromet.2016.10.011.
Minerals 2022, 12, 1014 18 of 19

7. Mohan, D.; Pittman, C.U., Jr. Arsenic removal from water/wastewater using adsorbents—A critical review. J. Hazard. Mater.
2007, 142, 1–53. https://doi.org/10.1016/j.jhazmat.2007.01.006.
8. Jia, Y.; Demopoulos, G.P. Adsorption of Arsenate onto Ferrihydrite from Aqueous Solution: Influence of Media (Sulfate vs
Nitrate), Added Gypsum, and pH Alteration. Environ. Sci. Technol. 2005, 39, 9523–9527. https://doi.org/10.1021/es051432i.
9. Demopoulos, G. On the preparation and stability of scorodite. In Proceedings of the TMS Annual Meeting, San Francisco, CA,
USA, 1 January 2005; pp. 25–50.
10. Wang, H.-J.; Gong, W.-X.; Liu, R.-P.; Liu, H.-J.; Qu, J.-H. Treatment of high arsenic content wastewater by a combined physical–
chemical process. Colloids Surf. A Physicochem. Eng. Asp. 2011, 379, 116–120. https://doi.org/10.1016/j.colsurfa.2010.11.047.
11. White, T.J.; Eaton, G.F.; Kyle, J.; Lincoln, F. Xtaltite—A Mineralogical Approach to the Disposal of Mercury and Arsenic Wastes.
In Extraction and Processing for the Treatment and Minimization of Wastes; The Minerals Metals & Materials Society: Warrendale,
PA, USA, 1994.
12. Zhu, Y.; Zhang, X.; Zeng, H.; Liu, H.; He, N.; Qian, M. Characterization, dissolution and solubility of synthetic svabite
[Ca5(AsO4)3F] at 25–45 °C. Environ. Chem. Lett. 2010, 9, 339–345. https://doi.org/10.1007/s10311-010-0284-0.
13. Twidwell, L.G.; McCloskey, J.W. Removing arsenic from aqueous solution and long-term product storage. JOM 2011, 63, 94–
100. https://doi.org/10.1007/s11837-011-0147-6.
14. Gilhotra, V.; Das, L.; Sharma, A.; Kang, T.S.; Singh, P.; Dhuria, R.S.; Bhatti, M.S. Electrocoagulation technology for high strength
arsenic wastewater: Process optimization and mechanistic study. J. Clean. Prod. 2018, 198, 693–703. https://doi.org/10.1016/j.jcle-
pro.2018.07.023.
15. Oh, C.; Ji, S.; Cheong, Y.; Yim, G. Applicability of electrochemical wastewater treatment system powered by temperature di
ference energy. J. Hazard. Mater. 2018, 351, 108–116. https://doi.org/10.1016/j.jhazmat.2018.02.026.
16. Riveros, P.; Dutrizac, J.; Spencer, P. Arsenic Disposal Practices in the Metallurgical Industry. Can. Met. Q. 2001, 40, 395–420.
https://doi.org/10.1179/cmq.2001.40.4.395.
17. de Klerk, R.J.; Feldmann, T.; Daenzer, R.; Demopoulos, G.P. Continuous circuit coprecipitation of arsenic(V) with ferric iron by
lime neutralization: The effect of circuit staging, co-ions and equilibration pH on long-term arsenic retention. Hydrometallurgy
2015, 151, 42–50.
18. de Klerk, R.J.; Jia, Y.; Daenzer, R.; Gomez, M.A.; Demopoulos, G.P. Continuous circuit coprecipitation of arsenic(V) with ferric
iron by lime neutralization: Process parameter effects on arsenic removal and precipitate quality. Hydrometallurgy 2012, 111–
112, 65–72.
19. Daenzer, R.; Xu, L.; Doerfelt, C.; Jia, Y.; Demopoulos, G.P. Precipitation behaviour of As(V) during neutralization of acidic
Fe(II)−As(V) solutions in batch and continuous modes. Hydrometallurgy 2014, 146, 40–47. https://doi.org/10.1016/j.hy-
dromet.2014.03.005.
20. Robins, R.G. Solubility and stability of scorodite, FeAsO4·2H2O: Discussion. Am. Mineral. 1987, 72, 842–844.
21. Caetano, M.L.; Ciminelli, V.S.; Rocha, S.D.; Spitale, M.C.; Caldeira, C.L. Batch and continuous precipitation of scorodite from
dilute industrial solutions. Hydrometallurgy 2009, 95, 44–52. https://doi.org/10.1016/j.hydromet.2008.04.010.
22. Min, X.-B.; Liao, Y.-P.; Chai, L.-Y.; Yang, Z.-H.; Xiong, S.; Liu, L.; Li, Q.-Z. Removal and stabilization of arsenic from anode slime
by forming crystal scorodite. Trans. Nonferrous Met. Soc. China 2015, 25, 1298–1306. https://doi.org/10.1016/s1003-6326(15)63728-
1.
23. Paktunc, D.; Bruggeman, K. Applied Geochemistry Solubility of nanocrystalline scorodite and amorphous ferric arsenate: Im-
plications for stabilization of arsenic in mine wastes. Can. J. Metall. Mater. Sci. 2010, 25, 674–683.
24. Verdugo, C.; Gomez, M.A.; Demopoulos, G.P. Study of arsenic release of atmospheric scorodite under reductive environments
Study of arsenic release of atmospheric scorodite in reductive environments. In Proceedings of the 4th International Seminar
on Process Hydrometallurgy, Hydroprocess, Santiago, Chile, 11–13 July 2012; pp. 86–94.
25. Das, A.; Mandal, A. Hydrogeochemical characteristics and its role in controlling arsenic mobilization in a shallow aquifer. Acta
Geochim. 2021, 40, 912–925. https://doi.org/10.1007/s11631-021-00479-x.
26. Guo, F.; Demopoulos, G.P. Development of an Encapsulation Process to Extend the Stability of Scorodite Under Wider pH and
Redox Potential Range Conditions. In The Minerals, Metals & Materials Series; Elsevier: Amsterdam, The Netherlands, 2018; pp.
1411–1420. https://doi.org/10.1007/978-3-319-95022-8_115.
27. Lagno, F.; Rocha, S.D.F.; Chryssoulis, S.; Demopoulos, G. Scorodite encapsulation by controlled deposition of aluminum phos-
phate coatings. J. Hazard. Mater. 2010, 181, 526–534. https://doi.org/10.1016/j.jhazmat.2010.05.046.
28. Leetmaa, K.; Guo, F.; Becze, L.; Gomez, M.A.; Demopoulos, G.P. Stabilization of iron arsenate solids by encapsulation with
aluminum hydroxyl gels. J. Chem. Technol. Biotechnol. 2014, 91, 408–415. https://doi.org/10.1002/jctb.4590.
29. Demopoulos, G.P. Aqueous precipitation and crystallization for the production of particulate solids with desired properties.
Hydrometallurgy 2009, 96, 199–214. https://doi.org/10.1016/j.hydromet.2008.10.004.
30. Wu, W.; Nancollas, G.H. Kinetics of nucleation and crystal growth of hydroxyapatite and fluorapatite on titanium oxide sur-
faces. Colloids Surf. B: Biointerfaces 1997, 10, 87–94. https://doi.org/10.1016/s0927-7765(97)00054-4.
31. Bluteau, M.C.; Becze, L.; Demopoulos, G.P. The dissolution of scorodite in gypsum-saturated waters: Evidence of Ca-Fe-AsO4
mineral formation and its impact on arsenic retention. Hydrometallurgy 2009, 97, 221–227.
Minerals 2022, 12, 1014 19 of 19

32. Gomez, M.; Becze, L.; Cutler, J.; Demopoulos, G. Hydrothermal reaction chemistry and characterization of ferric arsenate phases
precipitated from Fe2(SO4)3–As2O5–H2SO4 solutions. Hydrometallurgy 2011, 107, 74–90. https://doi.org/10.1016/j.hy-
dromet.2011.01.007.
33. Zhu, Y.; Zhang, X.; Chen, Y.; Xie, Q.; Lan, J.; Qian, M.; He, N. A comparative study on the dissolution and solubility of hydrox-
yapatite and fluorapatite at 25 °C and 45 °C. Chem. Geol. 2009, 268, 89–96. https://doi.org/10.1016/j.chemgeo.2009.07.014.
34. Wei, C.; Zhu, Y.; Yang, F.; Li, J.; Zhu, Z.; Zhu, H. Dissolution and solubility of hydroxyapatite and fluorapatite at 25 °C at
different pH. Res. J. Chem. Environ. 2013, 17, 57–61.