Hydrometallurgy 107 (2011) 74–90

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Hydrothermal reaction chemistry and characterization of ferric arsenate phases

precipitated from Fe2(SO4)3–As2O5–H2SO4 solutions
M.A. Gomez a,⁎, L. Becze a, J.N. Cutler b, G.P. Demopoulos a,⁎
a
McGill University, Department of Mining and Materials Engineering, 3610 University Street, Montreal, QC, Canada H3A2B2
b
Canadian Light Source Inc., University of Saskatchewan, 101 Perimeter Road, Saskatoon, SK, Canada

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

Article history: The hydrothermal reaction chemistry and characterization of high temperature (150–225 °C) ferric arsenate
Received 26 October 2010 phases produced from sulfate media was studied. In particular, the effect of Fe (III)/As (V) molar ratio,
Received in revised form 22 January 2011 temperature, and time on the phases formed was examined. Three major arsenate-bearing phases were
Accepted 24 January 2011
produced in our studies: (a) sulfate-containing scorodite (Fe(AsO4)1 − 0.67x(SO4)x·2H2O where x ≤ 0.20) at an
Available online 19 February 2011
Fe(III)/As(V) molar ratio of 0.7–1.87, 150–175 °C and 2–24 h reaction time; (b) ferric arsenate sub-hydrate
Keywords:
(FAsH; Fe(AsO4)0.998(SO4)0.01·0.72H2O) at Fe(III)/As(V) molar ratio of 0.69–0.93, 200–225 °C and 10–24 h
Fe–AsO4–SO4 system reaction time; (c) basic ferric arsenate sulfate (BFAS; Fe(AsO4)1 − x(SO4)x(OH)x·(1 − x)H2O, where
Autoclave 0.3 b x b 0.7) at Fe(III)/As(V) molar ratio of 1.67–4.01, 175–225 °C and 4–24 h reaction time. Scorodite was
High temperature (150–225 C) found to be metastable at an Fe(III)/As(V) molar ratio of one, 1 h reaction time and 200 °C. Extension of
Arsenic retention time to 10 h under the same conditions gave predominantly FAsH with minor presence of scorodite,
Raman and IR spectroscopy while additional retention time to 24 h resulted in the formation of only FAsH. XRD, Raman and ATR-IR,
XANES proved that our FAsH is the same phase with that labeled previously as “Type 1” and the “Phase 4”; similarly
Leachability
our BFAS was identical to the so-called “Type 2” and “Phase 3”. The Fe L-edge XANES analysis showed that
Gold and copper industries
scorodite, FAsH and BFAS exhibited an octahedral type of crystal field with a paramagnetic high spin anti-
CESL
Total pressure oxidation ferromagnetic character as in hematite. Short term leachability tests determined FAsH to be slightly more
soluble than scorodite and BFAS after 24 h, while after several TCLP-like contacts there was b 0.1 mg/L arsenic
release from all phases. Long term (N 8 months) stability testing of FAsH and BFAS found FAsH to yield
somewhat higher arsenic release than BFAS. The latter's arsenic release potential was evaluated to be
equivalent or slightly better than that of scorodite.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction precipitation and characterization of Fe(III)–AsO4 compounds from

Autoclave processing of copper and/or gold-bearing mineral
feedstocks is associated with the in-situ precipitation of iron (III)
arsenates (Berezowsky et al., 1999; Dymov et al., 2004). These
precipitates report with the leach residues into tailings ponds.
Therefore, characterization and evaluation of the arsenic release
(leachability) of these iron (III) arsenates is of great environmental
interest.
In contrast to the poorly crystalline Fe(III)–AsO4 waste solids
produced by co-precipitation during normal neutralization of hydro-
metallurgical process effluents (Langmuir et al., 1999; Moldovan et al.,
2003; Jia and Demopoulos, 2008; Chen et al., 2009), controlled
precipitation (Filippou and Demopoulos, 1997; Singhania et al., 2006)
or autoclave processing leads to the precipitation of crystalline phases.
Swash and Monhemius (1994) were the first to report on the
⁎ Corresponding authors. Tel.: +1 514 398 2046; fax: +1 514 398 4492.
E-mail addresses: mario.gomez@mail.mcgill.ca (M.A. Gomez),
george.demopoulos@mcgill.ca (G.P. Demopoulos).
sulfate solutions – the type of solutions encountered in industrial
processes – under autoclave processing conditions. According to their
work four distinct crystalline phases were found to form: scorodite,
FeAsO4·2H2O; basic iron sulfate, FeOHSO4 (BFS); “Type1”, Fe2
(HAsO4)3·zH2O with z b 4; and “Type 2”, Fe4(AsO4)3(OH)x(SO4)y
with x + 2y = 3. The formation of these phases was correlated to tem-
perature (150° to 225 °C) and Fe(III) to As(V) molar ratio (1/1–9/1)
and fixed retention time of 24 h. Thus according to these authors, Type
1 formed in the whole temperature range 150 °C to 225 °C, when Fe
(III)/As(V) molar ratio b1.5. Scorodite was reported to form at 150 °C
and 175 °C when Fe(III)/As(V) ratio N1.5. Finally Type 2, in mixture
with basic iron sulfate, was reported to form at 200 °C ≤ T ≤ 225 °C and
Fe(III)/As(V) ratio N1.5. Of the two new phases, only “Type 2”
(b0.34 mg/L As) was found to meet the TCLP leachability criterion
exhibiting similar behavior with scorodite (b0.8 mg/L As).
More recently, Dutrizac and Jambor (2007) reported on an
extensive experimental program involving the precipitation of Fe
(III)–AsO4–SO4 phases in the temperature range of 175–225 °C. In
their program, the effects of time (1–24 h), initial acidity (0 to 0.71 M

0304-386X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.01.007
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90
H2SO4) and variable Fe(III), As(V) concentrations were considered.
Characterization of the precipitated phases, which were all crystalline
in nature, identified two new phases in addition to scorodite
(FeAsO4·2H2O) and basic ferric sulfate (BFS: FeOHSO4). The two
new phases, labeled as “Phase 3” and “Phase 4”, were determined to
have the following stoichiometries respectively: Fe(AsO4)x(SO4)y
(OH) v (H 2 O) w where x + y = 1 and v + w = 1; and “Phase 4”,
FeAsO4·3/4H2O. Phase 3 was proposed to be a monoclinic polytype
of basic ferric sulfate produced via solid-solution uptake of AsO4.
Phase 3 precipitated at 175–210 °C, but mixtures of Phase 3 and BFS
were found to form at higher temperatures from solutions with Fe/
As ~ 4. At Fe/As molar ratio ~1 and 205 °C, Phase 4 was found to form
instead. Finally in the same work, it was found that scorodite
(containing a small amount of sulfate) formed in the 150–175 °C
range from solutions with initial Fe/As molar ratio ~ 3 (as calculated by
the present authors). Short term (40 h) leachability tests (terminal pH
in the range 3.5 to 4.5) that were conducted on the two new phases
yielded b0.1 mg/L As for Phase 3 and 1–3 mg/L As for Phase 4. This
observation led the authors to suggest that Phase 3 might be an
acceptable carrier for the disposal of arsenic.
From the above brief review, it becomes evident that the
hydrothermal Fe(III)–As(V)–SO4 system is very complex resulting in
the formation of different phases, the true identity and environmental
stability of which is a matter of industrial importance. In this study the
hydrothermal precipitation of iron (III) arsenate–sulfate phases is
revisited (a preliminary brief communication was made during the
Hydrometallurgy 2008 Conference by Gomez et al., 2008) with the
objectives of identifying the true nature of the precipitated iron (III)
arsenate phases via comprehensive characterization and correlating
their formation to prevailing solution chemistry in terms of reaction
stoichiometries and temperature. Furthermore, the obtained results
are compared to those of Swash and Monhemius (1994) as well as
Dutrizac and Jambor (2007) with the view of clarifying the apparent
differences between the two previous studies and contributing to the
fuller understanding of the overall chemistry of this system.
2. Experimental
2.1. Precipitation procedure
For the preparation of the starting solutions, analytical-reagent
grade As2O5·xH2O and Fe2(SO4)3·xH2O were dissolved in water in the
desired molar proportions (CFe = 0.30 M and CAs = 0.075–0.40 M) to
give different starting Fe(III) to As(V) molar ratios. The resulting
solutions (with natural pH ~ 1) were placed in a two-liter Parr
autoclave equipped with a glass liner. The solutions were then heated
(typical heat-up period ~45 min) to the desired temperature (150–
225 °C) and held there for different times (1, 4, 10 and 24 h) while
continuously stirred at 400 rpm. The resulting slurries were then
filtered after cooling using a pressure filter and a 0.1 μm filter paper.
Following thorough washing, the solids were subjected to character-
ization and leachability testing; the filtrate solutions were analyzed
for determination of their Fe, As, and S concentrations. All filtrates
were in addition titrated to determine their free sulphuric acid
concentration.
2.2. Characterization methods
X-ray Diffraction (XRD), ATR-IR, Micro-Raman, Thermo Gravimet-
ric Analysis (TGA), Field Emission Gun Scanning Electron Microscopy
(FEG-SEM), X-ray absorption near-edge spectroscopy (XANES) and
Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES)
techniques were used to identify the nature of the materials.
The XRD analysis was performed with a Rigaku Rotaflex D-Max
diffractometer equipped with a rotation anode, a copper target (λ Cu
Kα = 1.5046 Å), a monochromator composed of a graphite crystal and
75
a scintillator detector. The diffractometer used 40 kV and 150 mA. The
scans were recorded between 5 and 100° 2θ with a 0.1° step size and
an acquisition time of 3 s/step. XRD simulations were done with the
crystallographic software CaRIne (version 3.1, Boudias and Monceau,
1998) using our experimental calculated lattice parameters and the
published atomic positions from Hawthorne (1976) for Scorodite and
Jakeman et al. (1991) for FAsH.
Infrared spectra were obtained using a Perkin Elmer FTIR
(Spectrum BX model) spectrometer with a Miracle single bounce
diamond ATR cell from PIKE Technologies. Spectra over the 2000–
550 cm− 1 range were obtained by the co-addition of 200 scans with a
resolution of 4 cm− 1 at the FWHM of the internal Polystyrene
strongest C–H vibration.
Raman Microscopy was conducted on a Renishaw Invia micro-
scope using the 50× short distance objective and a polarized argon
laser operating at 514 nm operating at 10% of the laser power at the
microscope exit. An average of 10 scans was obtained from 4000 to
150 cm− 1 to improve the resolution and the statistics of the
collection.
The number of crystallization waters was determined with a TGA
Q500 from Thermal Analysis Instruments. The acquisition was done
between 20 and 900 °C with a heating rate of 10 °C/min. The purge gas
used was nitrogen.
The morphological characterization of the three phases was done
on the Field Emission Gun Scanning Electron Microscope (FEG-SEM)
Hitachi S-4700. Prior to the morphological analysis, the produced
solids were deposited on carbon double sided tape and coated with a
thin layer of AuPd.
The X-ray Absorption Near Edge Structure (XANES) spectra were
recorded using the sample current in total electron yield mode using
the spherical grating monochromator (SGM) beamline at the
Canadian Light Source (University of Saskatchewan, Canada). The
beam line is equipped with a Dragon-type spherical grating
monochromator and was designed for high spectral resolution studies
(Regier et al., 2007). The spectroscopic resolving power (E/ΔE) is
estimated to be greater than 3200. Reagent grade hematite (α-Fe2O3)
and melanterite (FeSO4·7H2O) from Fisher Scientific (98% + purity)
were used as standards for Fe+ 3 and Fe+ 2 oxidation states. The Fe L-
edge spectra were normalized using a single normalization method
and the energy scale of our compounds was calibrated to the main L3
peak of hematite (α-Fe2O3) occurring at 709.5 eV (Garvie et al., 1994;
van Aken et al., 1998; van Aken and Liebscher, 2002; van Aken and
Lauterbach, 2003; Otero et al., 2008). The spectra were obtained from
696 to 736 eV using a coarse step size of 0.5 eV before the first edge
and a smaller step of 0.04 eV at the main absorption edges.
Solutions and digested solid products were subjected ICP-AES
analysis with a Thermo Jarrel Ash Trace Scan machine. Standards of 0.5,
5.0 and 50 mg/L of each element (Fe, As and S) and a blank (4 vol.%
HNO3) were use to calibrate the instrument. The standard deviation in
each case was found to be less than 5% by running the same sample at
least three times. Prior to ICP-AES analysis the solids were digested in
HCl (25 vol.%) solution (500 mg solids in 100 mL solution) heated at
70 °C. The dissolution was complete after 30 min.
2.3. Short and long term arsenic release
Both short-term and long-term leachability tests were performed.
The short-term tests involved using a solid to liquid ratio of 1 to 40
(5 g/200 ml) using multiple (up to 7) TCLP contacts of 24 h each at
pH ~ 5 (using NaOH and HNO3) as described previously (Bluteau and
Demopoulos, 2007). Such multiple-contact TCLP testing ensures
collection of data that better reflect the stability of the crystalline
phase(s) under investigation. In addition to the TCLP tests, long term
leachability tests at target pH values of 3, 5 and 7.5 were carried out on
FAsH and BFAS for the purpose of evaluating their long term arsenic
release behavior. The pH of these longer term tests was adjusted
76 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90

periodically to their target value via the use of NaHCO3 or HNO3, and
samples were taken periodically and analyzed for arsenic via the use
of ICP-AES.
3. Results and discussion
The precipitation of iron (III) arsenate–sulfate phases was
investigated over the temperature range 150–225 °C. Typically
0.3 M Fe(SO4)1.5 solutions containing arsenic (V) at various molar
ratios (0.7 ≤ Fe(III)/As(V) ≤ 4) were treated from 1 to 24 h. There were
three iron (III) arsenate phases found to form: (1) sulfate-substituted
scorodite [Fe(AsO4)1 − 0.67x(SO4)x·2H2O] (where 0.00 ≤ x ≤ 0.22) (2)
ferric arsenate sub-hydrate (FAsH) [FeAsO4·0.75H2O], and (3) basic
ferric arsenate sulfate (BFAS) [Fe(AsO4)1 − x(SO4)x(OH)x·wH2O]. First
their precipitation chemistry and domain of formation (i.e. precipi-
tation conditions in terms of temperature, Fe(III)/As(V) molar ratio,
time and acid concentration range) for each of the phases is described,
followed by their structural and molecular characterization as well as
their short and long term leachability response.
3.1.1. Iron and arsenic precipitation
Analysis of the precipitation data (Table 1) revealed that at least
90% of the arsenic had precipitated under all conditions tested except
for the case with the Fe/As molar ratio in the initial solution being less
than 1. On the other hand the degree of percent iron precipitation was
much lower than that of arsenic when the Fe/As ratio in solution was
above 1. This behavior upon further analysis in terms of molar ratio of
“precipitated As/Fe ratio” was determined to indicate that iron
precipitated in tandem with arsenic (at a molar ratio Fe/As essentially
one), i.e. no precipitation of other iron (III) phases took place; this is
further confirmed with the detailed characterization data reported
later. This is better demonstrated with the help of Fig. 1a, where the
initial molar ratio of Fe/As in solution is plotted against the molar ratio
of As/Fe precipitated. As it can be seen the collected experimental data
fall into line with slope 1.3. As discussed later (refer to composition
data in Table 2), the produced scorodite was slightly deficient in
arsenate content due to small incorporation of sulfate thus explaining
in part the deviation of the experimental data from the theoretical
slope of 1 in Fig. 1a.

3.1. Precipitation of scorodite 3.1.2. Acid generation

The precipitation conditions associated with the formation of
scorodite are summarized in Table 1. On the same Table, the
precipitation efficiency for each of the elements Fe and As, as well
as the molar ratios of precipitated As/Fe ratio and acid generated/
arsenic precipitated are shown. Scorodite was found to form (all
characterization-identification data is presented in the following
section) in the temperature range 150–175 °C with Fe(III)/As(V)
ratios 0.70 to 1.8 and independent of retention time (1 to 24 h). It is
also worthy to remark here that scorodite was found to form at 200 °C,
when the Fe(III)/As(V) = 1, as an intermediate (metastable) phase.
Thus hydrothermal precipitation after 1 h yielded scorodite with
presence (25%) of FAsH. Extension of hydrothermal processing to 10 h
(more on this later on) yielded a predominantly FAsH product with
minor presence of scorodite, while at 24 h there was only FAsH
present. This means that from a kinetics point of view scorodite forms
quickly but because of lack of thermodynamic stability (at N175 °C) it
converts with time to FAsH by subsequent dehydration:
FeAsO4 ·2H2 O→FeAsO4 ·0:75H2 O + 1:25H2 O
Interestingly enough according to Swash and Monhemius (1994)
scorodite was supposed to be produced only at Fe (III)/As(V) N 1.5 for
similar otherwise conditions ([Fe+ 3] = 0.3 M, 150–175 °C, no initial
acid addition and 24 h). Instead these authors reported the formation
of the so called Type 1 phase (Fe2(HAsO4)3·zH2O) under the same
conditions we found scorodite.
The precipitation of scorodite is associated with acid generation.
As per data in Table 1, the acid concentration in the final solution
varied from 0.27 to 0.56 M in comparison to an initial pH of ~ 1. The
final acid concentration was found to be in direct correspondence to
the amount of precipitated arsenic. Thus upon calculation of the molar
ratio “H2SO4 generated/As precipitated” (refer to Table 1) a mean
value of 1.47 ± 0.11 was obtained corresponding to the following
reaction stoichiometry (Eq. (2)), where w = 2 for scorodite:
FeðSO4 Þ1:5 + H3 AsO4 + wH2 O→FeAsO4 ·wH2 O + 1:5H2 SO4 ð2Þ
3.1.3. Chemical composition
Table 2 summarizes the composition data for the various scorodite
products. The mean chemical composition was: 24.44 ± 0.88% Fe,
57.22 ± 3.73% AsO4, 3.44 ± 2.60% SO4, and 15.33 ± 1.22% H2O yielding
the following empirical formula: Fe(AsO4)0.94(SO4)0.08·1.95H2O. It is
interesting to note the incorporation of a small fraction of sulfate
within the crystal structure of scorodite; this has been confirmed via
ð1Þ
vibrational spectroscopy as reported elsewhere (Gomez et al., 2010).
As a consequence of the small substitution of sulfate into scorodite, the
Fe/As molar ratio was slightly higher than one (refer to data in Table 2).
The corresponding ratio Fe/(As + S) that takes into account the sulfate
substitution, on the other hand, was essentially one: 0.98 ± 0.06
(Table 2). Hence the general molecular formula of the sulfate-
substituted scorodite becomes: [Fe(AsO 4 ) 1 − 0.67x (SO 4 ) x ·2H 2 O]
(where 0.00 ≤ x ≤ 0.20).

Table 1
Scorodite hydrothermal precipitation data.

Experimental conditions Results

Exp Fe/As Time Temp Final H2SO4 Precipitation efficiency Molar ratios
ID ratio (h) (°C) (M)
Fe (%) As (%) Precipitation As/Fe ratio H2SO4(gen)/As(ppt)

Sc-1 0.70 10 175 0.56 96.6 69.6 0.73 0.49/0.29 = 1.69

Sc-2a 0.91a 1a 200a 0.49 100 92 0.92 0.42/0.29 = 1.46
Sc-3 0.93 24 175 0.45 95 87.6 0.92 0.38/0.26 = 1.48
Sc-4 0.94 10 175 0.47 95.3 87.1 0.91 0.40/0.25 =1.57
Sc-5 0.97 24 160 0.46 n/a 99 n/a 0.39/0.25 = 1.55
Sc-6 1.50 10 150 0.30 68.1 96.8 1.42 0.23/0.16 = 1.43
Sc-7 1.60 2 175 0.27 73.5 97.3 1.32 0.20/0.15 = 1.33
Sc-8 1.60 24 175 0.26 75.5 98.3 1.30 0.20/0.15 = 1.33
Sc-9 1.87 10 150 0.27 60.0 97.8 1.63 0.20/0.137 = 1.45
Sc-10 0.96 24 175 0.45 98.6 92.2 0.93 0.40/0.29 = 1.37
a
Presence (25%) of FAsH was detected.
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90 77

a ization later) are summarized in Table 3. In this series of tests no

2.0 external acid was added. On the same Table, the precipitation
efficiency for each of the elements Fe and As, as well as the molar
1.8 ratios of “precipitated As/Fe ratio” and “acid generated/arsenic
Initial Fe/As molar ratio

precipitated” are shown. FAsH was found to form at both 200 and
1.6 225 °C with Fe(III)/As(V) ratios 0.70 to 1.1 and reaction time 10–24 h.
At Fe(III)/As(V) ≥1.7 and the same otherwise temperature/time
1.4 range and no acid addition, basic ferric arsenate sulfate (BFAS—more
on this later, Table 5) was formed. As explained in Section 3.1.3,
y = - 0.31 +1.38x
1.2 external acid addition or reaction time extension was found to favor
R = 0.98
the formation of FAsH at the expense of BFAS. As such it may be
1.0 deduced that the transition between FAsH and BFAS formation over
the temperature range 200–225 °C lies at a ratio ~1.3–1.5.
0.8 As previously mentioned, at 200 °C and a reaction time of 1 h,
scorodite formed ahead of FAsH, which apparently converted to the
0.6 latter upon extension of the reaction time as per Eq. (1). Under the
0.6 0.8 1.0 1.2 1.4 1.6 same conditions (200–225 °C and Fe(III)/As(V) ~ 1) but with 24 h
Precipitated As/Fe molar ratio reaction time, Swash and Monhemius (1994) found “Type 1” to form.
On the other hand, Dutrizac and Jambor (2007) found “Phase 4”
b 1.0 formed after 3 h at Fe(III)/As(V) ~ 1 and 205 °C in the presence of
externally added acid (0.4 M).
Similar to scorodite, iron and arsenic precipitated at a ratio
essentially one (see Fig. 1b) with arsenic (V) “taking down” iron (III).
Initial Fe/As molar ratio

No evidence of additional co-precipitated arsenic-free ferric (hy-

droxy) oxide phase was apparent. The precipitation of FAsH was
associated once more with acid generation—refer to Table 3. Accord-
0.8 ing to the stoichiometry of reaction (2), 1.5 mol of H2SO4 were
expected for each mole of arsenic precipitated. The experimental
y = - 0.37 +0.92x values collected were somewhat lower than that expected (refer to
R = 0.97 Table 3) with a mean at 1.32 ± 0.2.

3.2.2. Chemical composition

Table 4 summarizes the composition data for the various ferric
0.6 arsenate sub-hydrate (FAsH) products. The mean chemical composition
0.6 0.7 0.8 0.9 1.0 was: 26.75 ± 0.95% Fe, 67.25 ± 0.50% AsO4, 0.45± 0.17% SO4, and 6.0 ±
Precipitated As/Fe molar ratio 0% H2O yielding the following empirical formula: Fe(AsO4)0.998
(SO4)0.01·0.72H2O. It is interesting to note the much lower crystalliza-
c 3.5 tion water content hence the chosen name “sub-hydrate” adopted in
this work in analogy of other hydrated crystals like those of CaSO4·xH2O
(Ling and Demopoulos, 2005). Another apparent difference with
3.0 scorodite is the much lower substitution (practically nil) of sulfate
within the crystal structure of FAsH, pointing to the significant structural
differences between the two phases as discussed further later.
2.5
(Fe/As) solid

3.3. Precipitation of basic ferric arsenate sulfate (BFAS)

2.0
At Fe(III)/As(V) molar ratio N1.5 (and up to 4—the maximum ratio
tested) basic iron (III) arsenate sulfate (Fe(AsO4)x(SO4)y(OH)z·wH2O)
1.5
y = 0.10+0.98x was found to form at temperatures 175 °C (and higher) when no acid
R = 0.97 was externally added after 4 to 24 h reaction time. Under the same
conditions of Fe(III)/As(V) molar ratio and T ≥ 200 °C, Swash and
1.0 Monhemius (1994) reported the formation of Type 2 plus basic ferric
1.0 1.5 2.0 2.5 3.0 3.5 sulfate (FeOHSO4) with the amount of the latter phase increasing with
(Fe/As) ppt the increase of Fe(III)/As(V) molar ratio. In their study, no acid was
externally added to the initial solution while the retention time was
Fig. 1. (a) Plot of Fe/As molar ratio in initial solution against molar ratio of precipitated 24 h. On the other hand Dutrizac and Jambor (2007) who carried out
As/Fe molar ratio in the case of scorodite precipitation (data from Table 1). (b) Plot of their experiments in the presence of externally added acid (typically
Fe/As molar ratio in initial solution against molar ratio of precipitated As/Fe in the case ~0.4 M H2SO4), found Phase 3 to form after 3 to 4 h reaction time at
of FAsH precipitation (data from Table 3). (c) Plot of (Fe/As)solid against (Fe/As) ppt for 205 °C. At higher temperatures (225 °C) or longer time (N6 h) and Fe
BFAS precipitation (data from Table 5).
(III)/As(V) ratio ~4 (or higher) basic ferric sulfate in addition to Phase
3 were reported to form. In this work however, we did not detect the
3.2. Precipitation of ferric arsenate sub-hydrate (FAsH) presence of basic ferric sulfate using the techniques employed herein.

3.2.1. Precipitation 3.3.1. Precipitation of iron and arsenic

The precipitation conditions associated with the formation of this The amount of arsenic precipitated was in the order of 90 to 93% for
crystallization water-deficient ferric arsenate (more on its character- all tests except those performed at 225 °C. This is rather unexpected as
78 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90

Table 2
Chemical composition data for scorodite.

Solid composition

Exp ID Fe (%) AsO4 (%) SO4 (%) H2O (%) Fe/As ratio Fe/As + S ratio H2O/Fe ratio

Sc-1 24 61 6 15 1.02 0.857 1.93

Sc-2a 25 62 0 17a 1.00 1.00 2.10
Sc-3 24 59 1 15 1.01 0.99 1.93
Sc-4 24 57 1 15 1.05 1.02 1.93
Sc-5 26 59 1 13 1.09 1.07 2.14
Sc-6 25 59 5 17 1.05 0.94 2.23
Sc-7 25 54 6 15 1.15 0.99 1.86
Sc-8 23 52 6 15 1.10 0.94 2.02
Sc-9 24 52 5 16 1.15 1.01 2.07
Avg 24.44 ± 0.88 57.22 ± 3.73 3.44 ± 2.60 15.33 ± 1.22 1.06 ± 0.06 0.98 ± 0.06 2.02 ± 0.12
Total sum from averages = 100.43 ± 4.78
a
Presence (25%) of FAsH was detected.

Table 3
FAsH hydrothermal precipitation data.

Experimental conditions Results (FAsH)

Exp Fe/As Time Temp Final H2SO4 Precipitation efficiency Molar ratios
ID ratio (h) (°C) (M)
Fe (%) As (%) Precipitation As/Fe ratio H2SO4(gen)/As(ppt)

Fs-1 0.69 10 200 0.54 98.6 64.1 0.65 1.60

Fs-2 0.76 10 225 0.44 98.9 77.6 0.78 1.25
Fs-3 0.89 10 225 0.51 98.9 85.2 0.86 1.31
Fs-4 0.93 24 200 0.44 98.4 88.4 0.90 1.13
Fs-5a 1.10a 10a 200a 0.49a 93.3a 96.8a 1.04a 1.30a
a
Denotes the presence of residual (20%) scorodite in addition to FAsH.

Table 4
Chemical composition data for FAsH.

Solid composition

Exp ID Fe (%) AsO4 (%) SO4 (%) H2O (%) Fe/As ratio Fe/As + S ratio H2O/Fe ratio

Fs-1 26 67 0.3 6 0.96 0.958 0.716

Fs-2 28 68 0.3 6 0.89 0.875 0.664
Fs-3 27 67 0.6 6 1.00 0.989 0.689
Fs-4 26 67 0.6 6 0.96 0.952 0.715
Fs-5a 27a 64a 0.6a 16a 1.05a 1.035a 1.084a
Avg 26.75 ± 0.95 67.25 ± 0.50 0.45 ± 0.17 6±0 0.95 ± 0.04 0.94 ± 0.04 0.70 ± 0.04
Total Sum from averages = 100.45 ± 1.16
a
Denotes the presence of residual (20%) scorodite in addition to FAsH.

higher temperatures are known to promote precipitation. Hence, the
225 °C data should be considered as tentative. Nevertheless, if any error
were involved in the analysis this applied equally to iron, so comparative
evaluation of the iron and arsenic precipitation is still possible. The
amount of iron precipitated in general was lower than that of arsenic
especially at the higher Fe/As ratio of ~4. Upon calculating the number of
moles of Fe and As precipitated, the ratio (Fe/As)ppt was determined as
shown in Table 5. It can be seen this ratio to vary from 1.5 to 3 reflecting
the different amount of arsenate contained in this phase—to be
discussed in the next section.

Table 5
Precipitation data for BFAS.

Experimental Conditions Results

Exp Fe/As Time Temp Final Precipitation Molar ratios

ID ratio (h) (°C) H2SO4 efficiency
(M)
Fe (%) As (%) (Fe/As) ppt (Fe/As) solid ðH2 SO4 Þgen H2 SO4 1:5−x 1:5−x
ðAsÞppt Fe 1−x 1
Ba-1 1.67 4 225 0.27 79.8 76.4 1.75 1.78 1.97 1.12 1.88 1.07
Ba-2 1.79 10 175 0.32 82.4 89.7 1.64 1.66 2.01 1.20 1.83 1.1
Ba-3 1.77 10 200 0.34 81.9 93.6 1.55 1.66 1.45 1.09 1.83 1.1
Ba-4 1.82 10 175 0.33 76.6 91.4 1.52 1.43 1.63 1.00 1.71 1.20
Ba-5 1.84 10 225 0.35 88.1 91.3 1.77 1.61 2.01 1.14 1.80 1.1
Ba-6 1.88 24 225 0.34 80.0 83.6 1.73 1.69 2.02 1.13 1.85 21.0
Ba-7 3.53 10 225 0.26 78.9 85.6 3.25 2.90 2.77 0.85 2.47 90.8
Ba-8 3.70 10 200 0.22 68.6 92.6 2.74 2.50 1.76 0.66 2.25 40.9
Ba-9 4.01 10 175 0.22 53.6 93.5 2.29 2.32 1.97 0.81 2.16 00.9
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90 79

Table 6
Chemical composition data for BFAS.

Solid composition

Exp ID Fe (%) AsO4 (%) SO4 (%) H2O (%) As Fe x SO4 a Fe H2 O

Fe As + S Fe
Ba-1 28 39 18 10 0.56 0.44 0.37 (14.7%) 1.17 1.11
Ba-2 29 43 17 10 0.60 0.40 0.34 (15.0%) 1.17 1.07
Ba-3 31 46 22 9 0.60 0.40 0.41 (2.50%) 1.07 0.90
Ba-4 29 50 13 10 0.70 0.30 0.26 (13.3%) 1.14 1.07
Ba-5 30 46 17 11 0.62 0.38 0.33 (13.1%) 1.15 1.14
Ba-6 28 41 17 10 0.59 0.41 0.35 (14.6%) 1.16 1.11
Ba-7 31 26 31 9 0.34 0.66 0.58 (12.1%) 1.18 0.90
Ba-8 32 32 28 10 0.40 0.60 0.51 (15.0%) 1.19 0.97
Ba-9 31 33 26 10 0.43 0.57 0.49 (14.0%) 1.19 1.00
Avg 29.88 ± 1.4 39.55 ± 7.8 21 ± 6.1 9.88 ± 0.6 0.54 ± 0.12 0.46 ± 0.12 0.40 ± 0.10 (12.7 ± 3.9%) 1.16 ± 0.03 0.93 ± 0.34
Total sum from averages = 100.31 ± 1.0
a
Denotes% discrepancy from x.

3.3.2. Acid generation
The precipitation of BFAS was accompanied by acid (H2SO4)
generation. The molar ratios of acid generated over arsenic and iron
precipitated were determined and reported in Table 5. According to
this data, the precipitation reaction generates ~2 mol of H2SO4 per
mol of As(V) precipitated or ~ 1 mol acid per mol of iron (III)
precipitated. To account for these observations the following
reaction (3) is proposed. The stoichiometry of BFAS is validated in
the next section:
FeðSO4 Þ1:5 + ð1−xÞH3 AsO4 + wH2 O→FeðAsO4 Þ1−x ðSO4 Þx ðOH Þx ·wH2 O
+ ð1:5−xÞH2 SO4
ð3Þ
The x is determined in Table 6. If the above reaction stoichiometry
were correct then the ratios (1.5 − x)/(1 − x) and (1.5 − x)/1 should
be close to the experimentally measured acid/As and acid/Fe molar
ratios respectively, which indeed is the case as can be verified with the
data of Table 5.
3.3.3. Chemical composition
Table 6 summarizes the composition data for the various basic
ferric arsenate sulfate (BFAS) products. The percent iron and water
contents were essentially constant at ~ 30% and ~10% respectively,
while the arsenate and sulfate contents varied in connection to each
other. The interrelationship of arsenate and sulfate variation is better
appreciated with the plots presented in Fig. 1c. It can be seen that as
the Fe/As ratio in solution increases from ~ 1.7–2 to 3.5–4, the amount
of arsenate in the solids decreases while the amount of sulfate
correspondingly increases. This behavior is indicative of solid solution
composition as was initially proposed by Dutrizac and Jambor (2007)
and confirmed via molecular characterization recently by the present
authors (Gomez et al., 2010).
By determining the molar ratios of As/Fe (or equivalently Fe/As),
SO4/Fe, Fe/(As + S) and H2O/Fe of the various BFAS solids (data in
Table 6), the empirical formulae summarized in Table 7 were
obtained. In these formulae a fraction of the water content is assigned
as OH for charge balance purposes. It can be seen, within the inevi-
table deviation due to experimental measurement, that [AsO4] + [SO4]
is near one which implies that OH from a charge balance point of
view should have the same stoichiometric coefficient with SO4, what
we have chosen to call “x”. This stoichiometric coefficient was found
to vary (data in Table 6) from 0.3 to 0.6. This differs as much as 15%
from the experimentally determined SO4/Fe ratio (data in Table 6)
hence a rather reasonable match. Using x and applying the restrictions
[AsO4] + [SO4] = 1 and [OH] + [H2O] = 1, the theoretical formula was
determined for each of these BFAS products as shown in Table 7.
The generic solid solution formula, therefore for BFAS becomes:
Fe(AsO4)1 − x(SO4)x(OH)x·(1 − x)H2O, where 0.3 b x b 0.7.
By comparison Dutrizac and Jambor's (2007) formula of their
Phase 3 varied from Fe0.8–1.1(AsO4)0.25(SO4)0.75(OH)y to Fe0.8–1.1
(AsO4)0.54(SO4)0.46(OH)y, while that of Swash and Monhemius
(1994) Type 2 phase was [Fe4(AsO4)3(OH)x(SO4)y with x + 2y = 3].
It is clear that the formula proposed by Swash and Monhemius (1994)
did not recognize the existence of the solid composition behavior as
they used a fixed Fe/As ratio of 1.33. On the other hand Dutrizac and
Jambor's (2007) formula pointed elementally towards the solid
solution composition as confirmed in the present work and further
proved spectroscopically elsewhere (Gomez et al., 2010). In the case
of Dutrizac and Jambor's (2007) formula the Fe(III)/As(V) ratio varied
from 1.5–4.4 while in the present work varied from 1.4 to 3.
3.3.4. BFAS conversion to FAsH
As mentioned earlier BFAS was found to form at Fe(III)/As(V) ≥ 2
and T ≥ 200 °C while at Fe(III)/As(V) b 2 FAsH was found to precipitate
instead. In all of these tests, no acid was externally added to the
starting solutions. Thus when the test at Fe(III)/As(V) = 1.7–1.8 and
225 °C was repeated in the presence of 0.3 M externally added H2SO4
it was found that FAsH formed instead of the expected BFAS after 10 h
retention time. The respective precipitation efficiencies were 85.3% As

Table 7
Empirical and theoretical formulae of the various BFAS products.

Exp ID Empirical formula x Theoretical formula

Ba-1 Fe(AsO4)0.56(SO4)0.38(OH)0.56·0.54H2O 0.44 Fe(AsO4)0.56(SO4)0.38(OH)0.56·0.54H2O

Ba-2 Fe(AsO4)0.60(SO4)0.34(OH)0.54·0.42H2O 0.40 Fe(AsO4)0.60(SO4)0.40(OH)0.40·0.60H2O
Ba-3 Fe(AsO4)0.60(SO4)0.34(OH)0.52·0.38H2O 0.40 Fe(AsO4)0.60(SO4)0.40(OH)0.40·0.60H2O
Ba-4 Fe(AsO4)0.70(SO4)0.26(OH)0.38·0.68H2O 0.30 Fe(AsO4)0.70(SO4)0.30(OH)0.30·0.70H2O
Ba-5 Fe(AsO4)0.62(SO4)0.33(OH)0.48·0.66H2O 0.38 Fe(AsO4)0.62(SO4)0.38(OH)0.38·0.62H2O
Ba-6 Fe(AsO4)0.59(SO4)0.35(OH)0.53·0.57H2O 0.41 Fe(AsO4)0.59(SO4)0.41(OH)0.41·0.59H2O
Ba-7 Fe(AsO4)0.34(SO4)0.58(OH)0.82·0.08H2O 0.66 Fe(AsO4)0.34(SO4)0.66(OH)0.66·0.34H2O
Ba-8 Fe(AsO4)0.40(SO4)0.51(OH)0.78·0.19H2O 0.60 Fe(AsO4)0.40(SO4)0.60(OH)0.60·0.40H2O
Ba-9 Fe(AsO4)0.43(SO4)0.49(OH)0.73·0.27H2O 0.57 Fe(AsO4)0.43(SO4)0.57(OH)0.57·0.43H2O
80 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90
and 58.5% Fe. By comparison in the absence of externally added acid
(data in Table 5) the corresponding efficiencies were 100% As and
88.7% Fe. Calculation of the molar ratio of precipitated (Fe/As)ppt gave
1.20 in the presence of acid (formation of FAsH) versus 1.77 in the
absence of acid (formation of BFAS). This may imply that increasing
acid concentration promotes the formation of FAsH at the expense of
BFAS.
In other words, it is hypothesized that the formation of BFAS is
kinetically favored and that given the right hydrothermal conditions
in terms of temperature and time would transform to FAsH. This was
verified by performing an additional test at 200 °C and Fe(III)/As(V)
molar ratio of 2 but this time employing an initial acidity of 0.3 M and
72 h retention time. Analysis of the final product showed to be FAsH
with the following empirical formula: Fe(AsO4)0.99·0.73H2O. The final
acidity in this test was 1.1 M H2SO4. The following reaction is
proposed to describe the transformation of BFAS to FAsH:
FeðAsO4 Þ1−x ðSO4 Þx ðOHÞx ·ð1−xÞH2 O
+ 0:5xH2 SO4 →ð1−xÞFeAsO4 ·0:75H2 O + xFeðSO4 Þ1:5
+ ð0:25 + 0:75xÞH2 O
The above metastability of BFAS and its conversion to FAsH was
not reported previously. Dutrizac and Jambor (2007) who studied the
effect of acid concentration did that at 205 °C and 3 h retention time.
Apparently under those conditions given the slow transformation of
BFAS to FAsH this went unnoticed; similarly it may be projected that
BFAS would not transform in industrial autoclaves given the short
retention time employed (~60 min). However, this may not be the
case if the operating temperature were pushed well above the 225 °C
tested here as seems to be the recent industrial trend. Under such
elevated temperature (N225 °C) conditions some FAsH may form at
the expense of BFAS, an event that can have consequences on the
arsenic release (leachability) of the produced precipitates—this is
discussed in a later section.
3.4. Precipitation of arsenate-bearing basic ferric sulfate (As-BFS)
Dutrizac and Jambor (2007) were the first, extrapolating from the
ground breaking work of Ventruti et al. (2005), to suggest that BFAS
(Phase 3 in their case) is a monoclinic polytype of BFS formed via
arsenate uptake by BFS. The same authors reported that the
orthorhombic BFS compound could accommodate up to 9.8 mass%
AsO4. With the view of studying the similarities and differences
between BFAS and arsenate containing BFS a sample of the latter
was prepared under the following synthesis conditions: Fe/As =
12 ([Fe(SO4)1.5] = 0.96 M, [H3AsO4] = 0.08 M), no free acid, 220 °C
Fig. 2. The Gomez–Becze–Demopoulos (“GBD”) Precipitation Diagram of the arsenate phases found in the Fe (III)–AsO4–SO4 system.
and 5 h. The produced arsenate bearing BFS had the following com-
position: 30% Fe, 52% SO4, 2% AsO4, 10% OH and 5% H2O. By comparison
the theoretical composition of BFS is 33.1% Fe, 56.8% SO4 and 10% OH.
3.5. Precipitation diagram
Inspired from the earlier phase diagram published by Swash and
Monhemius (1994) we have constructed a new precipitation diagram
that gives the domain of formation of the three ferric arsenate phases
in terms of the Fe(III)/As(V) molar ratio in the solution and the
temperature. This is shown in Fig. 2.
There exist certain significant differences with the one published
by Swash and Monhemius (1994). Thus according to Swash and
Monhemius (1994), scorodite formation occurs only at Fe (III)/As
(V) N 1.5 in the same temperature range (150–175 °C) as in our
diagram. At Fe(III)/As(V) ratios of 1–1.5 and temperature of 150–
175 °C, these authors reported the formation of the so called Type 1
phase (Fe2(HAsO4)3·zH2O), which is shown in the characterization
ð4Þ section to be the same with our FAsH. However, in our studies under
the same conditions (Fe(III)/As(V) ratios of 1–1.5 and 150–175 °C)
only scorodite was found to form. At higher temperatures (200–
225 °C and Fe(III)/As(V) ~ 1) there was agreement (considering
always Type 1 and FAsH equivalent) between the two works. In
contrast Dutrizac and Jambor (2007), found “Phase 4” to form after 3 h
processing at Fe(III)/As(V) ~ 1 and 205 °C in the presence of externally
added acid (0.4 M). As is shown in the characterization section Phase
4 is indeed the same with Type 1 and FAsH.
Another difference between Swash and Monhemius (1994)
diagram and the one built in this work is that basic ferric sulfate
(FeOHSO4) is reported to co-precipitate along their Type 2 phase
(same as our BFAS are shown later) even at Fe(III)/As(V) ratio of 2. On
the other hand Dutrizac and Jambor (2007) found their Phase 3
(equivalent to BFAS as shown later) to form after 3 to 4 h reaction
time at 205 °C. At higher temperatures (225 °C) or longer time (N6 h)
and Fe(III)/As(V) ratio ~ 4 (or higher) basic ferric sulfate (BFS) in
addition to Phase 3 was reported to form. No BFS was observed in this
work up to the Fe(III)/As(V) ratio tested using the analysis techniques
employed in this study.
Finally, there appears to be a discrepancy between the present
work and those previously published (Swash and Monhemius, 1994;
Dutrizac and Jambor, 2007) when it comes to the system of Fe(III)/As
(V) ≥ 2 at 175 °C. Thus in this work (see diagram in Fig. 2) BFAS was
found to form even at 175 °C (10 h retention time) when the Fe(III)/
As(V) ≥ 2, while Swash and Monhemius (1994) as well as Dutrizac
and Jambor (2007) reported instead the production of scorodite.
In the case of the former study (Swash and Monhemius, 1994) 24 h
retention time and no external acid was added, while in the latter
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90
(Dutrizac and Jambor, 2007) a shorter retention time of 5 h and
external acid (0.4 M H2SO4) was added to the starting solutions. It is
possible that the longer retention time and the use of acid promoted
the conversion of BFAS to scorodite in the case of the other works. In
this regard it is worthy to mention that other work by the present
authors reported elsewhere (Gomez et al., in review) found evidence
of the formation of an intermediate phase having the BFAS molecular
characteristics during precipitation of scorodite at 150 °C. These
observations serve to indicate that the diagram of Fig. 2 should not be
considered as absolute but rather as general guide recognizing that
the prevailing precipitation kinetics especially as far it concerns
supersaturation and short retention times can lead to deviations due
to metastable phase formation (Desiraju, 2007; Demopoulos, 2009).
4. Characterisation studies
In addition to chemical composition analysis (ICP-AES), the solid
products were further analyzed by several analytical techniques (TGA,
XRD, SEM, TEM, ATR-IR, Micro-Raman, and XANES). The detailed ATR-
IR and Raman vibrational analysis has been already published (Gomez
et al., 2010) and the crystallographic electron and X-ray synchrotron
based work is currently under way. Emphasis is given in the
characterization of the least known phases FAsH and BFAS and their
comparison to the phases labeled previously as Type 1, Type 2, Phase 3
and Phase 4.
4.1. TGA, XRD, ATR-IR and Raman analysis
Fig. 3 shows the thermogravimetric curves for scorodite, FAsH, and
BFAS. For scorodite, FAsH, and BFAS the average percent of
crystallization water was found to be 14.8%, 6.19%, and 9.80%,
respectively. These numbers are in close agreement with the
theoretical water contents of scorodite (15.6%) and FAsH (6.50%)
and the OH/H2O content of the BFAS formula (Tables 6 and 7)
determined in the previous section.
The three distinct phases, scorodite, FAsH and BFAS were
identified by XRD analysis (Fig. A1). Arsenate-containing basic ferric
sulfate was specifically synthesized for the purposes of comparison to
BFAS to see their structural similarities and differences.
4.1.1. Scorodite
The sulfate containing scorodite material exhibited good crystal-
linity and matched closely the JCPDS file for scorodite (No. 00-05-
0216) (Fig. 4). The d spacing was determined using Bragg's law, the
analysis was extended to the determination of the scorodite lattice
Fig. 3. TGA analysis of scorodite, ferric arsenate sub-hydrates (FAsH), basic ferric
arsenate sulfate (BFAS).
81
Fig. 4. XRD patterns obtained for experimental scorodite and reference JCPD file (005-
0216).
parameters assuming the orthorhombic structure and simulations via
the CaRIne software was done as in the case of scorodite produced by
hydrothermal synthesis from nitrate solutions (Le Berre et al., 2007)
but will not be discussed herein and are placed in the appendix files
(Tables A1–A2) for the reader. In general, there was excellent
agreement between the synthetic scorodite produced and that of
the data base as expected.
4.1.2. Ferric arsenate sub-hydrate (FAsH)
A similar procedure was followed for XRD characterization of the
produced FAsH and simulation of its structural model. The synthetic
material was in excellent agreement with the JCPDS file for FeAsO4·3/
4H2O (No. 01-081-1923); but in addition its XRD pattern showed
striking resemblance to the patterns of Phase 4 (sample kindly
supplied by Dutrizac and Jambor, 2007) and Type 1 (Swash and
Monhemius, 1994) (Fig. 5a). Table 8 lists the experimental peak
positions (d and 2θ values) and intensities in comparison to those of
the reference material. As it can be observed the reference and
experimental positions, both are in excellent agreement with one
another. The XRD analysis was extended to the determination of the
lattice parameters assuming the triclinic structure and using the d-
spacing equation for triclinic systems. The obtained values are given in
Table 9. The structure of our FAsH phase was further probed by using
the software Match! from Crystal Impact software (Brandenburg and
Putz, 2007). Once again it was found that FAsH corresponded to the
FeAsO4·3/4H2O compound first described by Jakeman et al. (1991).
Simulations were done with the software CaRIne (version 3.1)
using the experimental lattice parameters determined in this study
(Table 10) and the atomic positions given by Jakeman et al. (1991)
with the purpose to validate the structural model of FAsH. It is worth
noting that because of the way the atomic coordinates were
represented by Jakeman et al. (1991) (i.e. greater than one)
translations of ½ were made for all the coordinates before running
the simulation. Our ferric arsenate sub-hydrate like the FeAsO4·3/
4H2O compound possesses a triclinic structure in which the frame-
work of the crystal cell is composed of FeO6 octahedra and AsO4
tetrahedra. However, unlike scorodite (Hawthorne, 1976; Le Berre
et al., 2007), this hydrated ferric arsenate (FAsH) contains clusters of
four FeO6 octahedra through edge sharing to form Fe4O16(H2O)2
moieties, which are interconnected by corner sharing of AsO4
tetrahedra. The simulation and experimental data (only intensity
peaks N5 considered) is presented in Table 10. As it can be observed
the simulated XRD patterns are in excellent agreement with our
experimental work and the JCPDS reference pattern (No. 01-081-
1923). Moreover, the XRD patterns shown in Fig. 5a prove that
the FAsH phase [FeAsO4(0.99)·0.72H2O] produced in this work, Type 1
(Fe2(HAsO4)3·zH2O; reported by Swash and Monhemius (1994) and
82 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90

Table 8
a XRD of experimental FAsH compared to the XRD data of FeAsO4·3/4H2O (Jakeman et al.,
Ferric Arsenate sub-Hydrate (Fs-3)
1991).

Experimental ferric arsenate FeAsO4·3/4H2O JCPDS (01-081-1923)

sub-hydrate

2θ d (Å) Intensity 2θ d (Å) Intensity (hkl)

Phase 4 (As-184) 10.2 8.68 47 10.1 8.72 73.6 010

13.9 6.37 87 13.8 6.38 100 100
17.5 5.05 14 17.5 5.06 10.5 10−1
22.2 4.01 20 22.2 4.01 7.3 − 111
23.3 3.81 21 23.3 3.81 11.3 1−11
24.3 3.66 42 24.2 3.67 22.4 120
27.7 3.22 30 27.6 3.22 12.3 021
Type 1 (Swash 1994) 28.3 3.15 100 28.3 3.15 43.1 − 1−12
28.9 3.08 38 28.9 3.08 21.2 002
29.0 3.07 46 29.4 3.04 7.6 210
30.2 2.96 60 30.2 2.96 26.9 − 210
5 10 15 20 25 30 35 40 30.8 2.90 73 30.7 2.90 28.6 030
31.2 2.86 22 31.1 2.87 8.8 − 1−22
2θ 32.3 2.77 12 32.2 2.78 5.3 121
33.0 2.71 28 33.0 2.71 11.2 012
b 34.2 2.62 21 34.1 2.63 8.0 220
34.2 2.62 25. 34.4 2.60 7.0 − 130
34.4 2.61 21 34.6 2.59 4.5 − 2−12
35.2 2.55 20 35.1 2.55 7.6 102
42.8 2.11 21 42.8 2.11 5.8 1−32
44.1 2.05 18 44.1 2.05 6.7 − 311
45.2 2.00 18 45.2 2.00 5.5 − 222
FAsH (Fs-3) 56.4 1.63 24 56.4 1.63 6.1 − 1−14
58.2 1.58 31 58.2 1.58 4.3 − 411

FAsH (Fs-4)

found that indeed our produced FAsH and Phase 4 contain arsenate
Phase 4 (As-184)
units in the same molecular environment and exhibit the same site
and factor group symmetry as that described in detail elsewhere
Phase 4 (As-172) (Gomez et al., 2010; Gomez, 2011).

200 400 600 800 1000 1200 1400

Wavenumber (cm-1) 4.1.3. Basic ferric arsenate sulfate (BFAS)
To date there exist only limited structural and crystallographic
c data for this phase, thus the XRD analysis could only be made
empirically in this publication without resorting to theoretical
structural calculations. The detailed molecular (IR and Raman)
characterization of BFAS has been reported elsewhere (Gomez et al.,
2010; Gomez, 2011). The crystallographic (high resolution lab and
synchrotron based XRD) and atomistic (TEM-SAED) characterization
of the order–disorder (OD) behavior of this complex phase and its
FAsH (Fs-3)
relation to BFS is planned for a future publication.
FAsH (Fs-4) Table 11 gives a comparison of the peak positions (d-spacings) and
Phase 4 (As-184) intensity of BFAS, Type 2 (Swash and Monhemius, 1994), Phase 3
Phase 4 (As-172) (Dutrizac and Jambor, 2007) and our synthetic arsenate containing
FeOHSO4.
In general, it can be seen from Fig. 6a and Table 11, that Phase 3
and Type 2 are in excellent agreement with our BFAS in terms of peak
600 800 1000 1200 1400 1600 1800 2000 position and intensities; moreover it is worthy to note that BFAS/
Wavenumber (cm-1) Type2/Phase 3 are distinct in comparison to produced arsenate-
containing basic ferric sulfate in this study. It should be noted that
Fig. 5. (a) XRD of FAsH, Phase 4 and reference Type 1. (b) Raman of FAsH and Phase 4. Ventruti et al. (2005) found an OD (order–disorder) relationship for
(c) ATR-IR of FAsH and Phase 4. Johansson's (1962) FeOHSO4 structure. Only two MDO (Maximum
Degree of Order) polytypes were determined to be most favorable, a
monoclinic and an orthorhombic structure; these are geometrically
Phase 4 (described by Dutrizac and Jambor, 2007) are in fact the same
Table 9
phase having the structural characteristics of FeAsO4·3/4H2O com-
Experimental FAsH and reference FeAsO4·3/4H2O lattice parameter data (Jakeman
pound originally described by Jakeman et al. (1991). et al., 1991).
Moreover, to ensure that our FAsH was the same as the Phase 4
(for Type 1 unfortunately samples could not be obtained) at the Triclinic a (Å) b (Å) c (Å) α (Å) β (Å) γ (Å)

molecular level not just in terms of crystal structure, it was decided to Jakeman et al., 1991 6.60 9.01 6.54 104.39 104.40 84.25
investigate the arsenate bonding environment via the use of ATR-IR JCPDS (01-081-1923) 6.60 9.01 6.54 104.39 104.40 84.25
This work 6.60 9.01 6.57 104.38 104.40 84.25
and Raman spectroscopies. As can be observed in Fig. 5b–c, it was
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90 83

Table 10 spectroscopic data was given to support these claims or ideas. The
Comparison between XRD patterns obtained from the experimental FAsH product, the operation of such substitution (solid solution behavior) between
structure simulated with CaRIne and the reference FeAsO4·3/4H2O material (Jakeman
et al., 1991).
arsenate and sulfate in the case of BFAS was proved recently in
another publication via the collection of vibrational spectra (Gomez et
Ferric arsenate sub- Simulation with ferric FeAsO4·3/4H2O Plane al., 2010). In terms of powder XRD analysis, however, we found the
hydrate experimental arsenate sub-hydrate JCPDS (01-081- index
same diffraction patterns, i.e. the same crystal structures of BFAS at
pattern atom positions 1923)
various arsenate and sulfate contents from solids produced at Fe(III)
d (Å) d (Å) d (Å) (hkl)
to As(V) ratios equal to two or four and 175 to 225 °C; where in our
8.68 8.71 8.72 010 case we appear to be observing the other end of the solid-solution,
6.37 6.38 6.38 100 namely sulfate for arsenate substitution in the structure of BFAS.
5.05 5.07 5.06 10−1
4.01 4.01 4.01 − 111
Again to ensure that our BFAS was the same as the Phase 3 at the
3.81 3.82 3.81 1−11 molecular level not just in terms of crystal structure, we decided to
3.66 3.67 3.67 120 further probe the arsenate bonding environment via the use of ATR-IR
3.22 3.22 3.22 021 and Raman spectroscopies. Arsenic can be observed in Fig. 6b–c, it was
3.15 3.16 3.15 − 1−12
found that indeed our produced BFAS and Phase 3 (Dutrizac and
3.08 3.09 3.08 002
3.07 3.03 3.04 210 Jambor, 2007) contain arsenate and sulfate units in the same
2.96 2.96 2.96 − 210 molecular environment as that described in detail elsewhere
2.90 2.91 2.90 030 (Gomez et al., 2010). Again for Type 2, unfortunately samples could
2.86 2.87 2.87 − 1−22 not be obtained and thus only Phase 3 could be compared at the
2.77 2.78 2.78 121
2.71 2.72 2.71 012
molecular level but due to the structural similarities observed via
2.62 2.60 2.63 220 XRD, not much difference is expected.
2.62 2.59 2.60 − 130
2.61 2.56 2.59 − 2−12 4.1.4. Mixtures of Fe(III)–AsO4–SO4 phases
2.55 2.55 2.55 102
As it was noted in Section 3.1, the effect of time on the phase
2.11 2.12 2.11 1–32
2.05 2.05 2.05 − 311 formed is an important factor that previous studies (Swash and
2.00 2.01 2.00 − 222 Monhemius, 1994; Dutrizac and Jambor, 2007) neglected to consider
1.63 1.64 1.63 − 1−14 when investigating the same system. It is the purpose of this section to
1.58 1.58 1.58 − 411 provide the structural and spectroscopic proof of the mixed phases
found in this study.
As mentioned in the scorodite part (Section 3.1.1), scorodite was
unique and have nearly the same activation energy of formation with found to form at 200 °C, when the Fe(III)/As(V) = 1, as an interme-
the monoclinic form being slightly more favorable. The structure of diate (metastable) phase. Thus hydrothermal precipitation after 1 h
MDO1 results from a regular alternation of stacking operators (21/2 under these conditions yielded scorodite with presence (b25%) of
and 2− 1/2) and yields an orthorhombic structure. MDO2 on the other FAsH. The quantification of the phase was determined via XRD
hand results from a sequence of symmetry operators (21/2|21/2|21/2…) (Fig. 7a) using the integrated intensity relationship following a similar
and yields a monoclinic structure. procedure as that used in other published works (Kontoyannnis and
This relation was claimed to have been observed as well for the Vagenas, 2000; Dickinson and McGrath, 2001) while the use of ATR-IR
new Phase 3 by Dutrizac and Jambor (2007) via the tracing of a small and Raman spectroscopies (Fig. 7b–c) was only used to qualitatively
shoulder in their XRD; however, no peak positions were reported in observe the mixtures of the two phases that occurred in the samples.
that work. In BFAS/Phase 3, the polytypic proportions were claimed by The reason for not using these vibrational techniques to quantify the
Dutrizac and Jambor (2007) to be influenced by solid-solution amount of each phase in the mixtures is because it is well known for
substitution of arsenate for sulfate, which is greater in the monoclinic the ATR-IR technique, the intensity is not a fixed variable that may be
than the orthorhombic type. Yet, neither molecular nor structural controlled confidently (as concentrations vary) since the intensity of

Table 11
XRD data of experimental BFAS, Phase 3 (Dutrizac and Jambor, 2007), arsenate-containing BFS and reference Type 2 (Swash and Monhemius, 1994).

As-BFS As-BFS Type 2 Type 2 Phase 3 Phase 3 BFAS BFAS

This study This study Hydromet 94 Hydromet 94 Hydromet 07 Hydromet 07 This study This study
d (Å) Intensity d (Å) Intensity d (Å) Intensity d (Å) Intensity

4.84 17 4.89 5 4.84 18 4.87 7

3.61 100 3.38 100 3.61 14 3.66 5
3.35 83 3.25 64 3.35 100 3.36 100
3.24 28 2.64 19 3.24 62 3.25 36
3.16 16 2.35 6 3.16 26 3.19 20
2.60 45 2.32 20 2.60 18 2.62 19
2.32 41 2.06 15 2.32 17 2.33 13
2.24 17 1.89 9 2.24 10 2.28 6
2.06 13 1.76 2 2.06a 8 2.08 13
2.03 42 1.69 8 2.03 12 1.89 7
1.89 23 1.63 11 1.89 8 1.68 8
1.67 56 1.62 28 1.67 8 1.62 15
1.61 42 1.47 9 1.61 15 1.59 8
1.57 24 1.45 3 1.57 11 1.46 7
1.45 21 1.45 7 1.39 4
1.38 22 1.38 3 1.31 6
1.29 45 1.29 6 1.23 4
1.22 10 1.22 4
a
Indicates the shoulder used to trace the transition from BFS to Phase 3 (Dutrizac and Jambor, 2007).
84 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90

a a
Basic Ferric Arsenate Sulphate (Ba-5)
x x

Sc-4
Phase 3 (As-68)
x x
Type 2 (Swash 1994)

Sc-2
Arsenate-FeOHSO4 (McGill)

FeOHSO4 (Swash 1994)

Fs-3
5 10 15 20 25 30 35 40 45 50 55 60 65
2θ
10 20 30 40 50 60
2θ
b
b

Phase 3 (As-68) Fs-3

Phase 3 (As-72)

Sc-2

BFAS (Ba-5)
BFAS (Ba-8) Sc-4
200 400 600 800 1000 1200 1400
Wavenumber (cm-1) 200 400 600 800 1000 1200 1400
-1)
Wavenumber (cm
c
c
Fs-3

BFAS (Ba-5)
BFAS (Ba-8)
Sc-2
Phase 3 (As-72)
Phase 3 (As-68)

Sc-4
600 800 1000 1200 1400 1600 1800 2000
Wavenumber (cm-1)
600 800 1000 1200 1400 1600 1800 2000
Fig. 6. (a) XRD of BFAS, arsenate containing-BFAS, Phase 3, reference Type 2 and BFS. -1)
Wavenumber (cm
(b) Raman of BFAS and Phase 3. (c) ATR-IR of BFAS and Phase 3.

Fig. 7. (a) XRD of scorodite (Sc-4), scorodite + FAsH(Sc-2) and FAsH(Fs-3). (b) Raman of
the ATR-IR spectra can vary with the amount of pressure applied to scorodite (Sc-4), scorodite + FAsH(Sc-2) and FAsH(Fs-3). (c) ATR-IR of scorodite (Sc-4),
the sample, as well as the index of refraction of the material; in the scorodite + FAsH(Sc-2) and FAsH(Fs-3).

case of Raman spectroscopy, polarization effects (orientations), the

Raman cross sections and other factors may have an influence upon
the intensity of the peaks observed and thus may not be such a reliable
way to quantify binary or tertiary mixtures, as shown in the work of
Dickinson and McGrath (2001). However, vibrational spectroscopies
(ATR-IR and Raman) in this case did indeed show that our mixture
was composed of scorodite and FAsH but moreover that the
“dominant” phase was scorodite with some FAsH present as can be
observed from Fig. 7b–c.
Upon extension of hydrothermal processing to 10 h, at 200 °C and
Fe(III)/As(V) = 1, a predominantly FAsH product was obtained with
some minor scorodite (~20%). Again the amount of scorodite in this
mixture was determined via XRD (Fig. 8a) while the vibrational work
(Fig. 8b–c) was used to qualitatively observe the two phase
components of the mixture. It is interesting to note here however,
that in this case, the Raman spectra (Fig. 8b) showed no real scorodite
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90 85

a XRD and spectroscopic data presented in Fig. 9a–c. In this case owing
to the few diffraction lines BFAS exhibits, the XRD (Fig. 9a) of the
mixture shows only small peaks for BFAS since the FAsH phase has so
Sc-4 many lines in similar regions, making it difficult to determine the
amount of each phase confidently. Nevertheless, the ATR-IR and
Raman analysis clearly elucidated the presence of both phases as
shown in Fig. 9b–c.

Fs-5
a

Fs-3
Fs-3

10 20 30 40 50 60
2θ mixture

Fs-3 Ba-5

10 20 30 40 50 60
Fs-5 2θ

Sc-4
Fs-3
200 400 600 800 1000 1200 1400
Wavenumber (cm-1)

c mixture
Fs-3

Ba-5

Fs-5 200 400 600 800 1000 1200 1400

-1)
Wavenumber (cm

c
Sc-4 Fs-3

mixture
600 800 1000 1200 1400 1600 1800 2000

Wavenumber (cm-1) Ba-5

Fig. 8. (a) XRD of scorodite (Sc-4), FAsH + scorodite(Fs-5) and FAsH(Fs-3). (b) Raman of
scorodite (Sc-4), FAsH + scorodite(Fs-5) and FAsH(Fs-3). (c) ATR-IR of scorodite (Sc-4),
FAsH + scorodite(Fs-5) and FAsH(Fs-3).

component while the XRD (Fig. 8a) and ATR-IR (Fig. 8c) analysis
showed a contribution from both components.
As we reported in Section 3.3 BFAS was found to convert to FAsH 600 800 1000 1200 1400 1600 1800 2000
upon an increase in acid concentration or reaction time. However, the
Wavenumber (cm-1)
formation and occurrence of these two phases together has never
been reported by any previous work on this system (Swash and Fig. 9. (a) XRD of FAsH (Fs-3), FAsH + BFAS(mixture) and BFAS(Ba-3). (b) Raman of
Monhemius, 1994; Dutrizac and Jambor, 2007). The co-existence of FAsH (Fs-3), FAsH + BFAS(mixture) and BFAS(Ba-3). (c) ATR-IR of FAsH (Fs-3), FAsH +
these two high temperature phases is substantiated with the aid of the BFAS(mixture) and BFAS(Ba-3).
86 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90

4.2. Crystalline particle morphology

The different synthetic phases were characterized further by FEG-

SEM microscopy to investigate their particle size and morphology.
For scorodite, the FEG-SEM examination (Fig. 10a–b) showed at
low and high magnifications the particles to consist of aggregates of
individual sub-micron orthorhombic crystallites.
The ferric arsenate sub-hydrate (FAsH), the FEG-SEM study
(Fig. 11a–b) showed again the particles to consist of aggregates but
this time the individual crystallites were generally less than 1 μm
having the triclinic system features. It should be noted that in spite of
the structural and magnetic information reported by Jakeman et al.
(1991) on FeAsO4·3/4H2O, no SEM work was ever published on their
particle morphology until now.
For basic ferric arsenate sulfate (BFAS) (Fig. 12a–c), the morphol-
ogy and size of the particles was distinct in terms of overall look in
comparison to scorodite and FAsH. Here again we observe aggregates
of particles forming; however, now the individual crystallites were
larger in size (~ 2 μm). Furthermore, the physical appearance of the
crystals, that is the outward form of the internal structure of this
phase, appears in two shapes: a rounded type particle and a distinct
monoclinic–orthorhombic like crystal. From Fig. 12b, it can be
deduced that indeed they are the same phase (Fig. 12c), with one
grown to its full monoclinic–orthorhombic like form and the others
re-crystallizing to form its well defined crystal shape as to our delight
captured via our FEG-SEM studies.

4.3. Iron Fe L2,3 XANES

Finally the three iron (III) arsenate phases were characterized

using synchrotron-based techniques; in particular Fe L-edge X-ray

Fig. 11. FEG-SEM images of FAsH (Fs-3) at (a) 5× magnification. FEG-SEM images of
FAsH (Fs-3) at (b) 5× magnification.

Absorption Near Edge Structure (XANES) was employed. XANES

spectroscopy is an element-specific finger printing technique, which
probes the empty density of states in the system and sensitive to the
particular chemical and electronic environment of the compound of
interest (Koningsberger and Prins 1988; Colliex et al., 1991; de Groot,
2008; Otero et al., 2008; Huse et al., 2010) In general, the Fe L-edge
edge is influenced by crystal field effects, which in turn are affected by
the local symmetry around the absorbing iron atom in addition to
atomic multiplet and charge transfer effects (de Groot et al., 1990; de
Groot, 2005). Thus, Fe L-edge XANES may be used for qualitative
information of the local molecular environment around the absorbing
atom, in addition to oxidation state and electronic or magnetic
information (dichroism) (Otero et al., 2008; van Aken and Lauterbach,
2003; Huse et al., 2010).
Fig. 13 presents the Fe L-edge XANES spectra of reagent grade Fe+ 3
(α-Fe2O3) and Fe+ 2 (FeSO4·7H2O) in addition to those of the high
temperature synthetic Fe (III)–AsO4–SO4 phases (scorodite, FAsH and
BFAS), the former two were used to serve as references. In our case,
the spin-orbit splitting was used as an approximate value to ensure
that our oxidation states were around three as in the case of our
hematite standard, which they were in all cases. It is noted to the
reader that if more exact spin-orbit values are needed, Fe 2p XPS
analysis should be more suitable to get more exact values.

Fig. 10. FEG-SEM images of scorodite (Sc-4) (b) 20× magnification. FEG-SEM images of
scorodite (Sc-4) (b) 20× magnification.
4.3.1. Scorodite
The iron exists in a trivalent state and although much research has
been conducted on the As and Fe K-edges of scorodite (Waychunas
et al., 1993; Sherman and Randal, 2003; Moldovan et al., 2003; Chen
et al., 2009) there is little or no information on the Fe L-edge of this
common phase. However, as it has been shown for hematite (van
Aken et al., 1998; van Aken and Liebscher, 2002; van Aken and
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90
Fig. 12. FEG-SEM images of BFAS (Ba-5) at (a) 5× magnification. FEG-SEM images of
BFAS (Ba-5) at (b) 10× showing re-crystallization of the rounded particle to the
monoclinicorthorhombic like crystal. FEG-SEM images of BFAS (Ba-5) at (c) 20×
magnification showing the full monoclinic–orthorhombic like crystal.
Lauterbach, 2003), the Fe L-edge XANES may give new insights or
confirm other observations on the electronic/magnetic nature, ligand
environment and coordination geometry of the Fe+ 3 in this ferric
arsenate phase. The L2,3 maxima of the produced synthetic scorodite
(features D and B in Fig. 13) were observed at 723.2 eV(L2) and
709.5 eV(L3) respectively; their corresponding pre-peaks (features C
and A) occurred at 721.3 eV(L2) and 708.2 eV (L3) respectively
(Fig. 13). The transitions of the L3 edges have been assigned as Fe:
2p3/2 → Fe: 3d (t2g; eg) transitions; those of the L2 have been
suggested as transitions from Fe: 2p3/2 → Fe: 3d. The valency of the
Fe in scorodite as expected was trivalent. The separation between the
L2 and L3 edges due to spin-orbit coupling was found to be 13.7 ±
0.1 eV, in agreement with values reported for Fe+ 3 phases (Garvie
87
Fig. 13. Fe 2p XANES of scorodite, FAsH, BFAS, α-Fe2O3 and FeSO4·7H2O.
et al., 1994; van Aken et al., 1998; van Aken and Liebscher, 2002; van
Aken and Lauterbach, 2003).
From the Fe L-edge XANES spectra of scorodite it is clear that the
sharp pre-peak at low energy ~ 705 eV, which is indicative of
octahedral low spin Fe+ 3 compounds (Otero et al., 2008; Huse et
al., 2010), is not present in scorodite. Thus we can infer that the Fe+ 3
in scorodite in a paramagnetic high spin state (ground: 6A1g + 2T2g) in
an octahedral type of crystal field and an electronic configuration of
(t2g)3(eg)2 with a corresponding to an approximate 6S5/2 ground state
configuration (de Groot et al., 1990; de Groot, 2005). Moreover, since
we have a high spin state we can further deduce that in this case the
electron repulsions should dominate the ligand field effects and as
such we should have a weak field and small Δo. In addition, we can
infer that as in the case of hematite (van Aken and Lauterbach, 2003),
the ferric state in scorodite should be of a paramagnetic high spin anti-
ferromagnetic character. The metal–ligand coordination based on the
above findings should therefore be in a six fold environment in
agreement with previous reported crystallographic and EXAFS data
(Hawthorne, 1976; Chen et al., 2009).
4.3.2. Ferric arsenate sub-hydrate (FAsH)
The L2,3 maxima of the produced FAsH (features D and B) were
observed at 722.8 eV(L2) and 709.5 eV(L3); their corresponding pre-
peaks (features C and A) occurred at 721.1 eV(L2) and 708.0 eV (L3)
respectively (Fig. 13). The transitions of the L3 edges in FAsH have
been assigned as Fe: 2p3/2 → Fe: 3d (t2g; eg) transitions while those of
the L2 have been suggested as transitions from Fe: 2p3/2 → Fe: 3d. The
valency of iron in our produced synthetic FAsH is trivalent in
agreement with independent Mossbauer studies (Jakeman et al.,
1991); furthermore the separation between the L2 and L3 edges was
found to be 13.3 ± 0.1 eV in agreement with other Fe+ 3 phases
(Garvie et al., 1994; van Aken et al., 1998; van Aken and Liebscher,
2002; van Aken and Lauterbach, 2003).
The sharp pre-peak diagnostic of octahedral low spin Fe+ 3
compounds (Otero et al., 2008; Huse et al., 2010) is not present in
the Fe L-edge XANES spectra of FAsH (Fig. 13); once again suggesting
that the FAsH phase should exhibit a paramagnetic high spin anti-
88 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90
ferromagnetic character as in scorodite and hematite (van Aken and
Lauterbach, 2003) which is in agreement with Mossbauer studies
conducted by Jakeman et al. (1991). Again the ferric iron state in FAsH
is expected to be in an octahedral type of crystal field and an
electronic configuration of (t2g)3(eg)2 with a corresponding to an
approximate 6S5/2 ground state configuration (de Groot et al., 1990;
de Groot, 2005) and since a high spin character is observed, we expect
that the electron repulsions should dominate the ligand field effects
and as such we should have a weak field and small Δo.
4.3.3. Basic ferric arsenate sulfate (BFAS)
This is still a relatively unknown phase structurally, but as
mentioned recent studies have suggested that the crystal structure
could be monoclinic (Dutrizac and Jambor, 2007). However, no
crystallographic data has ever been published to confirm these
results; in our case, the synthetic products are fine powders and as
a result obtaining single crystal diffraction was not possible.
Therefore, by looking at the Fe L-edge of this phase we may obtain
new insights into the local chemical environment around the iron
(coordination geometry, high spin or low spin, ligand environment) of
this largely unknown phase.
In the case of the synthetic BFAS, the L2,3 maxima (features D and B
in Fig. 13) were observed at 722.8 eV(L2) and 709.5 eV(L3) while their
corresponding pre-peaks (features C and A) occurred at 721.1 eV(L2)
and 708.0 eV (L3) respectively. The L3 edges as before have been
proposed as Fe: 2p3/2 → Fe: 3d (t2g; eg); those of the L2 were assigned
to a Fe: 2p3/2 → Fe: 3d transition. The valency of the Fe in BFAS was
trivalent. The separation between the L2 and L3 edges was found to be
13.3 ± 0.1 eV in agreement with that of Fe+ 3 phases (Garvie et al.,
1994; van Aken et al., 1998; van Aken and Liebscher, 2002; van Aken
and Lauterbach, 2003).
As in the case of the other high temperature Fe(III)–AsO4–SO4
phases, the iron state in BFAS was found to be in a high spin state
(weak field, small Δo) and an in octahedral crystal type of field with a
possible (t2g)3(eg)2 electronic configuration and a metal (iron)–ligand
(oxygen) coordination that should be around six. Again the predicted
ground state configuration of the Fe + 3 in BFAS should be ~6S5/2 and
we expect a paramagnetic high spin anti-ferromagnetic character as
in hematite, scorodite and FAsH (van Aken and Lauterbach, 2003).
5. Short and long term leachability response
5.1. Short term arsenic release
Fig. 14 shows the sequential TCLP-like leachability response of
scorodite, FAsH and BFAS (details on the TCLP method used in this
Fig. 14. TCLP-like sequential test on scorodite, FAsH and BFAS.
study maybe found in Bluteau and Demopoulos, 2007). As it can be
seen after the first 24 h contact, scorodite and BFAS were well below
1 mg/L As but FAsH yielded about one order higher i.e. ~5 mg/L.
However, with subsequent contacting all samples yielded
values b 0.1 mg/L. The initial higher values measured for FAsH are
attributed to possible trace contamination (via co-precipitation of a
poorly crystalline phase or adsorption) which upon multiple contact-
ing was removed and representative data of the bulk phase was
obtained. Similar behavior was observed earlier by Bluteau and
Demopoulos (2007) for scorodite and Le Berre et al. (2007) for
mansfieldite. Swash and Monhemius (1994) showed similar results in
terms of short term arsenic release for their Type 2 and scorodite
phases produced, namely 0.34 mg/L and 0.8 mg/L of arsenic released
respectively, but much higher leachability (11.9 mg/L As) values were
obtained in the case of the Type 1 phase. On the other hand Dutrizac
and Jambor (2007) reported 0.1 mg/L of arsenic release for Phase 3
and 1–3 mg/L for Phase 4 after 40 h leachability testing with a
terminal pH of 3.2–3.8 and 4.2–4.5 respectively. The higher leach-
ability levels reported by Swash and Monhemius (1994) and Dutrizac
and Jambor (2007) for their phases corresponding to FAsH (Type 1
and Phase 4) may reflect the different inherent stability of those
phases or simply was the outcome of the applied testing procedure. In
their studies no pretreatment of the solids prior to leachability testing
was done as it was in this work (Fig. 14). However, it is understood
that the TCLP-type of testing provides only a comparative measure but
does not tell us much about the long-term arsenic release of a
particular phase and as such longer arsenic release measurements
were conducted, something not undertaken previously.
5.2. Long term arsenic release
Fig. 15a–c shows the long term arsenic release measurements at
nominal pH 3, 5 and 7.5 for the FAsH and BFAS phases along with their
corresponding measured pH values. In the case of the BFAS two
samples were tested, one with low sulfate content (Ba-4) and one
with high sulfate content (Ba-7). The purpose of this was to observe
whether the arsenic release of the BFAS phase was influenced by the
solid-solution behavior (composition) of the starting material. In all
cases essentially near equilibrium values were obtained as evident
from the plateau of the various curves, with the exception perhaps of
the test run at pH 8 (sample Ba-8, in Fig. 15c).
At pH 3 (Fig. 15a) a similar behavior to the TCLP test was observed,
namely the FAsH phase was found to yield slightly higher arsenic
release (0.67 mg/L) than that of the low and high sulfate content
BFAS. In terms of the BFAS, the values ranged from 0.27 mg/L (low
sulfate phase, Ba-4) to 0.1 mg/L (high sulfate phase, Ba-7). At pH 5
(Fig. 15b), the FAsH again gave the highest arsenic release (2.57 mg/L)
with the two BFAS samples giving identical values of only 0.1 mg/L (it
should be noted though that the pH of the high sulfate BFAS system
drifted and stabilized at 3.3 instead the target value of 5, in spite of the
fact it was always adjusted to the target pH of 5). By comparison the
equilibrium solubility of the sulfate-substituted scorodite (Sc-4) was
determined to be 0.6 mg/L As at pH 4.8 (equilibrium reached after
140 days; Gomez et al., 2008). This is slightly higher than the value
determined for the scorodite produced by hydrothermal precipitation
from nitrate media, namely 0.35 mg/L As at pH 5 (Bluteau and
Demopoulos, 2007).
Finally, at nominal pH 7.5 (Fig. 15c), FAsH and the low sulfate
content-BFAS (Ba-4) drifted to slightly lower equilibrium pH, namely
7.3 and 7.4 respectively at which the corresponding stable final
arsenic concentrations were 16.2 and 13.1 mg/L. On the other hand
the high sulfate content BFAS (Ba-7) system drifted initially down to
pH 3.5, which upon re-adjustment stabilized at pH 6.9 much lower
than the target pH 7.5. This prompted another pH adjustment that led
to overshooting and stabilization at pH 8. At this pH the arsenic
concentration was 66.2 mg/L. By comparison the corresponding long-
 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90 89

a than scorodite, while FAsH is less so. Nevertheless, in all cases it may
0.7 pH 3.0 pH 3.0 pH 3.0 pH 3.0 be deduced from the presented data that the disposal of these phases
pH 3.0
should be done at pH ~ 7 or lower to avoid significant arsenic release.
0.6
FAsH (Fs-3)
BFAS (Ba-5) 6. Conclusions
0.5 pH 3.0 pH 3.3
BFAS (Ba-8)
In this work, the hydrothermal reaction chemistry, detailed
As (mg/L)

0.4
characterization and experimental arsenic release behavior of ferric
pH 3.1
arsenate phases produced in the temperature range 150–225 °C from
0.3 pH 3.1 pH 3.2 pH 3.1
pH 3.2 sulfate media was reported. Here are the major conclusions from this
pH 2.8
research:
0.2

(1) The domain of formation of these phases depends upon four

0.1
pH 3.3 pH 2.7 pH 2.5 pH 2.6 pH 2.6 main experimental variables: temperature, Fe(III)/As(V) molar
ratio, acidity and time.
0.0
pH 2.9 pH 2.6 (2) There were four arsenate-bearing phases produced according
0 20 40 60 80 100 120 140 160 180 200 220 240 260 to the following conditions: (a) sulfate-containing scorodite
Time (days) (Fe(AsO4)1–0.67x(SO4)x·2H2O where x ≤ 0.20) at an Fe(III)/As
(V) molar ratio of 0.7–1.87, 150–175 °C and 2–24 h reaction
time; (b) ferric arsenate sub-hydrate (FAsH; Fe(AsO4)0.998
b pH 5.1 pH 5.1 pH 5.0 pH 5.1 (SO4)0.01·0.72H2O) at Fe(III)/As(V) molar ratio of 0.69–0.93,
2.5 200–225 °C and 10–24 h reaction time; (c) basic ferric arsenate
pH 5.3 sulfate (BFAS; Fe(AsO4)1 − x(SO4)x(OH)x·(1 − x)H2O, where
2.0 FAsH (Fs-3) 0.3 b x b 0.7) at Fe(III)/As(V) molar ratio of 1.67–4.01, 175–
pH 5.3
BFAS (Ba-5) 225 °C and 4–24 h reaction time; and (d) arsenate-containing
basic ferric sulfate (As-BFS) at high Fe/As molar ratio (~ 12).
pH 4.9 BFAS (Ba-8)
As (mg/L)

1.5 (3) Scorodite was found to be metastable at an Fe(III)/As(V) molar

ratio of one, 200 °C and one hour vis-à-vis FAsH. Extension of
1.0 reaction time to 10 h under the same conditions gave
predominantly FAsH with minor presence of scorodite. Finally,
additional retention time to 24 h resulted in the formation of
0.5 only FAsH.
pH 5.3 pH 5.3 pH 5.2 pH 5.2 (4) Upon external acid addition or extension of the reaction time at
pH 5.2 pH 5.0
0.0 temperature ≥200 °C, BFAS was found to convert to FAsH.
pH 2.8 pH 3.2 pH 2.8 pH 2.9 pH 3.3 pH 3.3
(5) Our FAsH and BFAS were found to be identical to the Type 1 and
0 20 40 60 80 100 120 140 160 180 200 220 240 260 Type 2 phases of Swash and Monhemius as well as the “new”
Time (days) Phase 4 and Phase 3 compounds produced by Dutrizac and
Jambor.
c 80
(6) Fe L-edge XANES of the produced ferric arsenate phases
(scorodite, FAsH and BFAS) indicated that they all exhibited a
pH 8.1 pH 8.0 paramagnetic high spin anti-ferromagnetic character similar to
pH 8.0
hematite.
60 pH 8.0
(7) Short term TCLP-like (pH 5 and 24 h) arsenic release measure-
FAsH (Fs-3) ments showed FAsH to be more soluble than scorodite after
BFAS (Ba-5) 24 h, while after subsequent TCLP contacts all phases were
As (mg/L)

40 BFAS (Ba-8) found to yield negligible amounts of arsenic (b1 mg/L).

(8) Long term arsenic release testing (~ 8 months duration)
determined FAsH to yield higher arsenic release than BFAS,
20 pH 6.9 pH 7.4 pH 7.3 pH 7.3 independent of the sulfate content of the latter. Thus at pH 5
pH 7.2 pH 7.3
the arsenic release level by FAsH was 2.5 mg/L but only 0.1 mg/
pH 7.6
pH 7.3 pH 7.3 pH 7.4 pH 7.4 L in the case of BFAS. The corresponding equilibrium value for
0 sulfate-substituted scorodite was 0.6 mg/L. At pH 7.3–7.4 the
pH 3.5 pH 6.9 corresponding values for FAsH and BFAS were 16 and 13 mg/L
respectively while that of scorodite is 13 mg/L. Hence for safe
0 20 40 60 80 100 120 140 160 180 200 220 240 260
disposal of these phases a pH of ~ 7 or lower are recommended.
Time (days)

Fig. 15. Long term arsenic release measurements for FAsH and BFAS with low (Ba-5)
and high (Ba-8) sulfate content at (a) pH 3. Long term arsenic release measurements for
FAsH and BFAS with low (Ba-5) and high (Ba-8) sulfate content at (b) pH 5. Long term
arsenic release measurements for FAsH and BFAS with low (Ba-5) and high (Ba-8)
sulfate content at (c) pH 7.5.
term leachability values of scorodite as obtained via interpolation
from the work of Bluteau and Demopoulos (2007) are 13 and
N100 mg/L at pH 7.3 and 8 respectively. This implies that BFAS
independent of its sulfate content is equally or slightly more stable
Acknowledgements
The support of this project by NSERC via a strategic project grant is
acknowledged as well as the sponsorship of the following companies:
Areva Resources Inc., Barrick Gold, Cameco, Hatch and Teck Cominco.
The authors are also grateful to staff at the SGM beam line and the
industrial science group (Tom Regier, Robert Blyth and Jeff Warner) at
the Canadian Light Source located at the University of Saskatchewan
for their technical support. Canadian Light Source is supported by
NSERC, NRC, CIHR, and the University of Saskatchewan. The authors
90 M.A. Gomez et al. / Hydrometallurgy 107 (2011) 74–90
would also like to thank Marie-Claude Bluteau and Jean-Francois Le
Berre for their past efforts in this project and Dr. Holger Putz from
Crystal Impact for running our XRD phases through the Match!
software. The authors also thank Samir Elouatik from the Materials
Surface Analysis Center at the University of Montreal and Petr
Fiurasek from the Center for Self Assemble Chemical Structures for
their technical support and the use of the Raman Microscope and ATR-
IR instruments. Finally we would like to thank J. E. Dutrizac for the
kind donation of Phase 3 and Phase 4 samples.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
doi:10.1016/j.hydromet.2011.01.007.
References
Berezowsky, R., Xue, T., Collins, M., Makwana, M., Barton-Jones, I., Southgate, M.,
Maclean, J., 1999. Pressure leaching of Las Cruces copper ore. J. Met. 51, 36–40.
Bluteau, M.-C., Demopoulos, G.P., 2007. The incongruent dissolution of scorodite —
solubility, kinetics and mechanism. Hydrometallurgy 87, 163–177.
Boudias, C., Monceau, D., 1998. Software CaRIne Crystallography, version 3.1. CaRine
Crystallography, Senlis, France.
Brandenburg, K., Putz, Holger, 2007. Crystal Impact—Software for Chemist and Material
Scientist. Match http://www.crystalimpact.com/match/Default.htm.
Chen, N., Jiang, D.T., Cutler, J., Kotzer, T., Jia, Y.F., Demopoulos, G.P., Rowson, J.W., 2009.
Structural characterization of poorly-crystalline scorodite, iron(III)-arsenate co-
precipitates and uranium mill neutralized raffinate solids using X-ray absorption
fine structure spectroscopy. Geochim. Cosmochim. Acta 73, 3260–3276.
Colliex, C., Manoubi, T., Ortiz, C., 1991. Electron-energy-loss-spectroscopy near-edge
fine structures in the iron–oxygen system. Phys. Rev. B 44 (11402-11), 420.
de Groot, F.M.F., Fuggle, J.C., Thole, B.T., Sawatzky, G.A., 1990. 2p X-ray absorption of 2d
transition-metal compounds: an atomic multiplet description including the crystal
field. Phys. Rev. B Condens. Matter 42, 5459–5468.
de Groot, F.M.F., 2005. Multiplet effects in X-ray spectroscopy. Coord. Chem. Rev. 249,
31–63.
de Groot, F.M.F., 2008. Ligand and metal X-ray absorption in transition metal
complexes. Inorg. Chim. Acta 361, 850–856.
Demopoulos, G.P., 2009. Aqueous precipitation and crystallization for the production of
particulate solids with desired properties. Hydrometallurgy 96, 199–214.
Desiraju, G.R., 2007. Crystal engineering: a holistic view. Angew. Chem. Int. Ed. 46,
8342–8356.
Dickinson, S.R., McGrath, K.M., 2001. Quantitative determination of binary and tertiary
calcium carbonate mixtures using powder X-ray diffraction. Analyst 126,
118–1121.
Dutrizac, J.E., Jambor, J.L., 2007. Characterization of the iron arsenate–sulphate
compounds precipitated at elevated temperatures. Hydrometallurgy 86, 147–163.
Dymov, I., Ferron, C.J., Phillips, W., 2004. Pilot plant evaluation of a hybrid biological
leaching—pressure oxidation process for auriferous arsenopyrite/pyrite feedstocks.
In: Collins, M.J., Papangelakis, V.G. (Eds.), Pressure Hydrometallurgy. CIM,
Montreal, Canada, pp. 735–750.
Filippou, D., Demopoulos, G.P., 1997. Arsenic immobilization by controlled scorodite
precipitation. J. Met. 49, 52–55.
Garvie, L.A.J., Craven, A.J., Brydson, R., 1994. Use of electron-energy loss near-edge fine
structure in the study of minerals. Am. Mineral. 79, 411–425.
Gomez, M.A., Becze, L., Bluteau, M.C., Le Berre, J.F., Cutler, J.N., Demopoulos, G.P., 2008.
Autoclave precipitation and characterization of Fe(III)–AsO4–SO4 phases. In:
Young, C.A., Taylor, P.R., Anderson, C.G., Choi, Y. (Eds.), Proceedings Hydrometal-
lurgy'08. SME, Littleton, pp. 1078–1085.
Gomez, M.A., Assaaoudi, H., Becze, L., Cutler, J.N., Demopoulos, G.P., 2010. Vibrational
spectroscopy study of hydrothermally produced scorodite (FeAsO4·2H2O), ferric
arsenate sub-hydrate (FAsH; FeAsO4·0.75 H2O) and basic ferric arsenate sulphate
(BFAS; Fe[(AsO4)1 − x(SO4)x(OH)x]·wH2O). J. Raman Spectrosc. 41, 212–221.
Gomez, M.A., Becze, L., Celikin, M., Demopoulos, G.P., in review. The effect of copper on
the formation of scorodite (FeAsO4·2H2O) from aqueous hydrothermal conditions:
evidence of a hydrated ferric cupric arsenate–sulfate short lived intermediate. J.
Colloid. Interf. Sci.
Gomez, M.A., 2011. Precipitation and Characterization of Arsenate Phases from Ca(II)–
Cu(II)–Fe(III)–AsO4–SO4 Hydrothermal Systems. Ph. D. Eng. Thesis, McGill
University, Montreal, Quebec, Canada.
Hawthorne, F.C., 1976. The hydrogen positions in scorodite. Acta Crystallogr. Sect. B
Struct. Sci. B32, 2891–2892.
Huse, N., Kim, T.K., Jamula, L., McCusker, J.K., de Groot, F.M.F., Schoenlein, R.W., 2010.
Photo-induced spin-state conversion in solvated transition metal complexes
probed via time-resolved soft X-ray spectroscopy. J. Am. Chem. Soc. 132,
6809–6816.
Jakeman, R.J.B., Kwiecien, M.J., Reiff, W.M., Cheetham, K., Torardi, C.C., 1991. A new
ferromagnetic orthoarsenate hydrate: structure and magnetic ordering of
FeAsO4·3/4H2O. Inorg. Chem. 30, 2806–2811.
Jia, Y.F., Demopoulos, G.P., 2008. Coprecipitation of arsenate with iron(III) in aqueous
sulphate media: effect of time, lime as base and co-ions on arsenic retention. Water
Res. 42, 661–668.
Johansson, G., 1962. On the crystal structure of FeOHSO4 and InOHSO4. Acta Chem.
Scand. 16, 1234–1244.
Koningsberger, D.C., Prins, R., 1988. X-ray Absorption: Principles, Applications,
Techniques of EXAFS, SEXAFS and XANES. John Wiley & Sons, New York.
Kontoyannnis, C.G., Vagenas, N.V., 2000. Calcium carbonate phase analysis using XRD
and FT-Raman spectroscopy. Analyst 125, 251–255.
Langmuir, D., Mahoney, J., MacDonald, A., Rowson, J., 1999. Predicting arsenic
concentrations in the pore waters of buried uranium mill tailings. Geochim.
Cosmochim. Acta 63, 3379–3394.
Le Berre, J.F., Cheng, T.C., Gauvin, R., Demopoulos, G.P., 2007. Hydrothermal synthesis
and stability evaluation of mansfieldite in comparison to scorodite. Can. Metall. Q.
46, 1–10.
Ling, Y., Demopoulos, G.P., 2005. Preparation of alpha-calcium sulfate hemihydrate by
reaction of sulfuric acid with lime. Ind. Eng. Chem. Res. 44, 715–724.
Moldovan, B.J., Jiang, D.T., Hendry, M.J., 2003. Mineralogical characterization of arsenic
in uranium mine tailings precipitated from iron rich hydrometallurgical solutions.
Environ. Sci. Technol. 37, 873–879.
Otero, E., Wilks, R.G., Regier, T., Bylth, R.I.R., Moewes, A., Urquhart, S.G., 2008. Sustituent
effects in the iron 2p and carbon 1s edge Near-Edge X-ray Absorption Fine
Structure (NEXAFS) spectroscopy of ferrocene compounds. J. Phys. Chem. A 112,
624–634.
Regier, T., Krochak, J., Sham, T.K., Hu, Y.F., Thompson, J., Blyth, R.I.R., 2007. Performance
and capabilities of the Canadian dragon: the SGM beamline at the Canadian Light
Source. Nucl. Instrum. Meth. A 582, 93–95.
Sherman, D.M., Randal, S.R., 2003. Surface complexation of arsenic(V) to iron(III)
(hydr)oxides: structural mechanism from ab initio molecular geometries and
EXAFS spectroscopy. Geochim. Cosmochim. Acta 67, 4223–4230.
Singhania, S., Wang, Q., Filippou, D., Demopoulos, G.P., 2006. Acidity, valency and third-
ion effects on the precipitation of scorodite from mixed sulfate solutions under
atmospheric-pressure conditions. Metall. Mater. Trans. B 37 B, 189–197.
Swash P.M. and Monhemius A.J., 1994. Hydrothermal precipitation from aqueous
solutions containing iron (III), arsenate and sulphate, In Proceedings Hydromet-
allurgy'94 (eds. Chapman & Hall). New York, N.Y., pp. 177–190.
van Aken, P.A., Liebscher, B., Styrsa, V.J., 1998. Quantitative determination of iron
oxidation states in minerals using Fe L2, 3-edge electron energy-loss near-edge
structure spectroscopy. Phys. Chem. Miner. 25, 323–327.
van Aken, P.A., Liebscher, B., 2002. Quantification of ferrous/ferric ratios in minerals:
new evaluation schemes of Fe L2, 3 electron energy-loss near-edge spectra. Phys.
Chem. Miner. 29, 188–200.
van Aken, P.A., Lauterbach, S., 2003. Strong magnetic linear dichroism in Fe L2, 3 and O
K electron energy-loss near-edge spectra of antiferromagnetic hematite α-Fe2O3.
Phys. Chem. Miner. 30, 469–477.
Ventruti, G., Scordari, F., Shiugaro, E., Gualtieri, A.F., Meneghini, C., 2005. The order–
disorder character of FeOHSO4 obtained from the thermal decomposition of
metahohmannite, Fe+ 2
3 (H2O)4[O(SO4)2]. Am. Mineralog. 90, 679–686.
Waychunas, G.A., Rea, B.A., Fuller, C.C., Davis, J.A., 1993. Surface chemistry of
ferrihydrite: part 1. EXAFS studies of the geometry of coprecipitated and adsorbed
arsenate. Geochim. Cosmochim. Acta 57, 2251–2269.