Chemie der Erde 78 (2018) 228–240

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Chemie der Erde

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Thermal behavior of ferric selenite hydrates (Fe2(SeO3)3·3H2O, T

Fe2(SeO3)3·5H2O) and the water content in the natural ferric selenite
mandarinoite
⁎
Astrid Holzheida, , Marina V. Charykovab, Vladimir G. Krivovichevb, Brendan Ledwiga,
Elena L. Fokinab, Ksenia L. Poroshinab, Natalia V. Platonovab, Vladislav V. Gurzhiyb
a
Institute of Geosciences, Kiel University, 24098 Kiel, Germany
b
Saint Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034 Russia

A R T I C L E I N F O A B S T R A C T

Handling Editor: Juraj Majzlan Any progress in our understanding of low-temperature mineral assemblages and of quantitative physico-che-
Keywords: mical modeling of stability conditions of mineral phases, especially those containing toxic elements like sele-
Selenites nium, strongly depends on the knowledge of structural and thermodynamic properties of coexisting mineral
Mandarinoite phases. Interrelation of crystal chemistry/structure and thermodynamic properties of selenium-containing mi-
Ferric selenite hydrates nerals is not systematically studied so far and thus any essential generalization might be difficult, inaccurate or
Thermogravimetry even impossible and erroneous. Disagreement even exists regarding the crystal chemistry of some natural and
Differential scanning calorimetry synthetic selenium-containing phases. Hence, a systematic study was performed by synthesizing ferric selenite
hydrates and subsequent thermal analysis to examine the thermal stability of synthetic analogues of the natural
hydrous ferric selenite mandarinoite and its dehydration and dissociation to unravel controversial issues re-
garding the crystal chemistry. Dehydration of synthesized analogues of mandarinoite starts at 56–87 °C and ends
at 226–237 °C. The dehydration happens in two stages and two possible schemes of dehydration exist: (a)
mandarinoite loses three molecules of water in the first stage of the dehydration (up to 180 °C) and the re-
maining two molecules of water will be lost in the second stage (> 180 °C) or (b) four molecules of water will be
lost in the first stage up to 180 °C and the last molecule of water will be lost at a temperature above 180 °C. Based
on XRD measurements and thermal analyses we were able to deduce Fe2(SeO3)3·(6-x)H2O (x = 0.0–1.0) as
formula of the hydrous ferric selenite mandarinoite. The total amount of water apparently affects the crystal-
linity, and possibly the stability of crystals: the less the x value, the higher crystallinity could be expected.

1. Introduction pollutants in soils and groundwater. Depending on its concentration,

Interest in selenium behavior under supergene conditions has in-
creased owing to needs of environmental protection. Near the surface,
selenium occurs in oxidized states as selenites (M-[SeO3]2−) and much
less frequently as selenates (M-[SeO4]2−). The basic sources of sele-
nium in near-surface environments are oxidation zones of selenides (M-
[Se]2−) or selenium-bearing sulfide deposits and technogenic waste
products. The Earth's surface and near-surface regions are dominated by
the interaction between minerals, aqueous solutions, and atmospheric
gases. Such interfaces play an important role in a number of geological
and geochemical processes. In an environmental context interfacial
processes such as mineral dissolution and mineral precipitation are
responsible for the release and/or confinement as well as the seques-
tration of selenium and heavy metals that may eventually become
selenium has a narrow concentration range between deficient and toxic
levels in the diets of humans and animals (see for more details, e.g.,
review papers by Plant et al., 2003, 2014). Since the selenium species
control Se mobility, bioavailability, and toxicity, it is essential to un-
derstand which of the common oxidation states of selenium prevail in
mineral phases under certain conditions and to disentangle the influ-
ence of parameters such as pH, redox potential, microbial activity and
the long-term impact of complexing and precipitating agents on the
release of Se to the environment. Recently we have characterized the
selenium oxysalts, selenites and selenates, as natural mineral systems,
reviewed and evaluated the accuracy of thermodynamic values of the
selenites formed during oxidation of selenides and selenium-bearing
sulfide minerals by examining the various experimental parameters
used, and proposed data on the thermodynamics of selenites at the

⁎
Corresponding author.
E-mail address: holzheid@min.uni-kiel.de (A. Holzheid).

https://doi.org/10.1016/j.chemer.2018.01.002
Received 27 September 2017; Received in revised form 1 January 2018; Accepted 16 January 2018
0009-2819/ © 2018 Elsevier GmbH. All rights reserved.
A. Holzheid et al.
standard state (25 °C, 1 bar pressure) (Charykova and Krivovichev,
2017; Krivovichev et al., 2017). In general, knowledge of the thermal
stability of hydrous selenites from the oxidation zone of ore deposits is
necessary in order to conduct a detailed analysis of their physico-
chemical formation conditions (Charykova et al., 2014, 2015, 2016;
Fokina et al., 2014). The objective of this study is thus to examine the
thermal stability of the synthetic analogue of natural hydrous ferric
selenite and its dehydration and dissociation.
Natural hydrous ferric selenite, mandarinoite, was found for the first
time at Pacajake mine, near Hiaco, Colquechaca, Bolivia (Dunn et al.,
1978), where it is associated with native selenium, siderite (FeCO3),
penroseite (NiSe2), and alteration products of selenides and selenium-
bearing sulfides such as ahlfeldite (NiSeO3∙2H2O), cobaltomenite (Co-
SeO3∙2H2O), chalcomenite (CuSeO3∙2H2O), and molybdomenite
(PbSeO3). The water content of mandarinoite was not directly analyzed
by Dunn et al. (1978), but the amount of water was derived from dif-
ference based on electron microprobe analysis
(Σ(Fe2O3 + SeO2) + H2O = 100.00 wt.%) and the theoretical formula
of the new mineral was deduced as Fe2(SeO3)3·4H2O.
Ferric selenite hydrates were also found in association with leached
quartz at the Skouriotissa mine, Cyprus, and in association with
poughite (Fe2(TeO3)2SO4·3H2O) at the El Plomo mine, Honduras (see
Hawthorne, 1984). A fourth occurrence was reported by Lasmanis et al.
(1981) at the De Lamar silver mine in Idaho, USA.
A single ferric selenite hydrate crystal from the De Lamar silver
mine was studied by Hawthorne (1984), who derived the ideal formula
of the mineral as Fe2(SeO3)3·6H2O from the structure based on single-
crystal X-ray precession photographs. A comparison of the mandar-
inoite composition deduced from electron microprobe analysis with the
formula deduced from the single-crystal X-ray precession photographs
is given in Table 1.
The Fe2O3 and SeO2 values from microprobe analysis (Dunn et al.,
1978) are ≈ 6% higher (6.3 and 6.0%, respectively) compared to the
values derived from the formula based on structure determination
(Hawthorne, 1984). This points to the fact that mandarinoite samples
studied by Dunn et al. (1978) may have lost water under the electron
beam during microprobe analysis. Thus, the Commission on New Mi-
nerals, Nomenclature and Classification of the International Miner-
alogical Association finally approved Fe2(SeO3)3∙6H2O as chemical
formula of the mineral mandarinoite (Pasero, 2017).
Rai et al. (1988) reported a synthetic analogue of mandarinoite with
the supposed formula Fe2(SeO3)3·6H2O. The value of the solubility
product obtained by Rai et al. (1995) was recommended by Olin et al.
(2005) in the reference book “Chemical thermodynamics of Selenium”.
However, Giester et al. (1996) reinvestigated compounds synthesized
by the method of Rai et al. (1988) and studied the synthetic phases by
chemical analysis, IR spectroscopy, powder and single crystal X-ray
diffraction as well as thermogravimetric analysis. Giester et al. (1996)
were able to show that the formula proposed by Rai et al. (1995) for
their synthetic product is erroneous and should be rewritten as
Fe2(SeO3)3·3H2O. The same formula was later confirmed by Larrañaga
et al. (2008).
In addition to Fe2(SeO3)3·3H2O and Fe2(SeO3)3·6H2O, information
about other Fe(III) hydrates is available in the literature and
Table 1
Compositions of natural hydrous ferric selenite.
microprobe, wt.%a structure, wt.%b Δ Δ, %
Fe2O3 28.68 26.86 28.68–26.86 = 1.82 6.3%
SeO2 59.53 55.98 59.53–55.98 = 3.55 6.0%
*H2O 11.79 17.16
Σ 100.00 100.00
a
Calculated by difference based on electron microprobe data, Dunn et al. (1978).
b
Derived from structure based on single-crystal X-ray precession photographs,
Hawthorne (1984).
229
Chemie der Erde 78 (2018) 228–240
summarized by Giester and Wildner (2006). For instance Giester (1993)
reports on synthesis and properties of Fe2(SeO3)3·H2ONishimura et al.
(2005) present XRD pattern similar to that depicted by Dunn et al.
(1978) and claim that the studied ferric selenite is Fe2(SeO3)3·4H2O
(quoted in the JCPDS Index No. 29-718). Thus, according to its struc-
tural characteristics there seems to be only one study (Nishimura et al.,
2005) in which a synthesized iron selenite hydrate matches with the
natural ferric selenite hydrate (mandarinoite of Dunn et al., 1978). But
Nishimura et al. (2005) do not satisfactorily clarify the number of water
molecules in mandarinoite, because – although the XRD pattern is in
agreement with Fe2(SeO3)3·4H2O – the authors report that chemical
analyses of the synthesized iron selenite hydrate point to 5 or 3 mole-
cules of water as function of temperature. Summarizing their results of
chemical and thermal analyses, Nishimura et al. (2005) conclude that
the stable solid phase changes from Fe2(SeO3)3·5H2O formed at a lower
temperature to Fe2(SeO3)3·3H2O as the temperature rises above 110 °C.
To shed light on ferric selenite hydrates regarding their possible
incorporation of water molecules and thermal behaviour, we performed
a systematic study by synthesizing ferric selenite hydrates and sub-
sequent thermal analysis.
2. Materials and methods
In total 20 syntheses of ferric selenite hydrates were successfully
accomplished by slow precipitation from aqueous solutions. At first we
followed the synthesis’ procedure described by Larrañaga et al. (2008),
but later modified the method by finally starting with only powdered
SeO2 (initial weight: ∼0.207 g) and FeCl3·6H2O (∼0.330 g) dissolved
in distilled water (26 ml). The solution was then placed in steel auto-
claves (length (L) 155 mm, outer diameter (OD) 55 mm, inner diameter
(ID) 35 mm) with teflon inlay (L 105 mm, OD 33 mm, ID 25 mm with a
total reactor volume of 55.75 ml). The entire reactors were heated up to
the desired run temperature in Memmert® heating ovens. Ferric selenite
hydrates formed under low-hydrothermal conditions (30–110 °C) and
autogenous pressure (1.5–2.7 bar). The pressure was calculated based
on the thermal expansion of the fluid in relation to the filling rate. Pre-
run pH values were in all experiments ∼1.06 and post-run pH values
∼1.11. Duration of synthesis varied between 5–259 days. Experiments
were terminated by removing the autoclaves from the heating oven.
The still sealed autoclaves were cooled down for ∼30 min under air
(except for experiments at only 30 °C) and finally opened. The solid
particles were filtered out, desiccated overnight at ∼47 °C, and stored
in an exsiccator until analysis. Sample recovery was 230 ± 50 mg.
Synthesis conditions, optical observation and XRD results are sum-
marized in Table 2.
The experimental charges were optically inspected by a scanning
electron microscope (CAMSCAN-Series-2-CS-44) and characterized by
X-ray powder diffractometry (Rigaku MiniFlexII and UltimaIV dif-
fractometers, CuKα1+2 radiation, 30 kV/15 mA (Rigaku MiniFlexII) and
40 kV/30 mA (UltimaIV), D-Tex Ultra PSD, 2theta degree step 0.02,
count time for each step 0.6 s, air). The chemical composition of solid
phases was measured using energy dispersive X-ray microanalysis on a
Hitachi S-3400N SEM. Thermal analyses with TG (thermogravimetry),
DTG (difference thermogravimetry) and DSC (differential scanning ca-
lorimetry) were done to detect the water amount and thermal behavior
of the synthesized phases. Various heating ramps are used (see figure
captions of Figs. 3–6 for more details). The results obtained were pro-
cessed using the program NETZSCH Proteus Thermal analysis version
5.2.1. The NETZSCH Peak Separation 2010.09 software was used for
additional processing of the DSC curve and separation of effects.
Thermogravimetric analysis combined with mass spectrometry allowed
to even measure the released volatile phases (NETZSCH STA 449 F3
Jupiter and Netzsch QMS 403C Aeolos). The thermal behavior of syn-
thetic ferric selenites hydrates was also studied in situ by High Tem-
perature X-ray Powder Diffraction (Rigaku Ultima IV powder dif-
fractometer with low-medium temperature camera R-300, CuKα1 + 2
A. Holzheid et al. Chemie der Erde 78 (2018) 228–240

Table 2
Synthesis conditions, optical obervations and XRD results of ferric selenite hydrates.

sample # pH temperature [°C] steam pressure [bar] duration [days] optical observations XRD results

1 1.16 110 ∼2.7 5 fine-grained yellow powder Fe2(SeO3)3·3H2O

2 1.10 110 ∼2.7 10 fine-grained yellow powder Fe2(SeO3)3·3H2O
3 1.23 110 ∼2.7 77 fine-grained yellow powder Fe2(SeO3)3·3H2O
4 1.26 110 ∼2.7 77 fine-grained yellow powder Fe2(SeO3)3·3H2O
5 0.97 110 ∼2.7 259 fine-grained (yellow)-green powder Fe2(SeO3)3·3H2O
6 1.11 110 ∼2.7 259 fine-grained (yellow)-green powder Fe2(SeO3)3·3H2O
7 1.07 75 ∼1.5 27 fine-grained lime-green powder Fe2(SeO3)3·3H2O
8 1.01 75 ∼1.5 27 fine-grained lime-green powder Fe2(SeO3)3·3H2O
9 1.02 30 ∼1.5 47 very fine-grained greenish powder mandarinoitea
10 1.10 30 ∼1.5 47 very fine-grained greenish powder mandarinoitea + Fe2(SeO3)3·3H2O
11 1.03 50 ∼1.5 47 very fine-grained greenish powder mandarinoitea + Fe2(SeO3)3·3H2O
12 1.07 50 ∼1.5 47 very fine-grained greenish powder mandarinoitea + Fe2(SeO3)3·3H2O
13 1.07 30 ∼1.5 34 very fine-grained greenish powder mandarinoitea
14 1.05 30 ∼1.5 34 very fine-grained greenish powder mandarinoitea
15 1,02 30 ∼1.5 69 very fine-grained greenish powder mandarinoitea
16 1.04 30 ∼1.5 69 very fine-grained greenish powder mandarinoitea
17 1.10 30 ∼1.5 61 very fine-grained greenish powder mandarinoitea
18 1.17 30 ∼1.5 61 very fine-grained greenish powder mandarinoitea
19 1.03 30 ∼1.5 61 very fine-grained greenish powder mandarinoitea
20 1.01 30 ∼1.5 61 very fine-grained greenish powder mandarinoitea

a
Synthetic analogue of mandarinoite.

radiation, 40 kV/30 mA, D-Tex Ultra PSD, vacuum, temperature step
5 K, heating rate 2 K/min).
3. Results and discussion
3.1. Sample characterization
The X-ray powder diffraction (XRD) patterns clearly indicate that
synthesized ferric selenite hydrates are either Fe2(SeO3)3∙3H2O or syn-
thetic analogues of mandarinoite, i.e. Fe2(SeO3)3∙6H2O (Fig. 1). The
unit-cell parameters calculated from the powder data are in good ac-
cordance with data obtained by other authors (Table 3). The agreement
of cell parameters with those reported for mandarinoite confirms suc-
cessful synthesis of ferric selenite hydrates with 6 molecules of H2O in
the ideal crystal structure usually at synthesis temperatures of 30 °C.
Based on the X-ray microanalyses Se:Fe ratios were derived with an
average Se:Fe ratio of 1.51 for Fe2(SeO3)3∙3H2O and of 1.52 for syn-
thetic analogues of mandarinoite, which corresponds to the stoichio-
metric ratio Se:Fe equal to 3:2. The amount of other elements was
below the detection limit with the exception of some samples with
traces of Cl, which apparently remained after synthesis with ferric
chloride. The small amount of Cl (less than 0.2%) was detected in
samples #10 and #11. As those samples consist of both ferric selenite
hydrates, Fe2(SeO3)3·3H2O and Fe2(SeO3)3·5H2O, the samples were not
further studied regarding the thermal behavior of the individual ferric
selenite hydrates Fe2(SeO3)3·3H2O and Fe2(SeO3)3·5H2O.
Fig. 2 illustrates post-run charges of Fe2(SeO3)3∙3H2O (Fig. 2A–C),
synthetic analogue of mandarinoite (Fig. 2F), and an intergrowth of
both ferric selenite hydrates (Fig. 2D–E). In general, higher synthesis
temperatures (75 and 110 °C) seem to result in precipitation of
Fe2(SeO3)3∙3H2O, intermediate temperatures of 50 °C form intergrowths
of both ferric selenite hydrates and the synthetic analogue of mandar-
inoite can be synthesized at the lowest temperature (30 °C), despite
different synthesis time at constant temperatures. Only in one sample
(sample #10) an intergrowth of both ferric selenite hydrates formed at
30 °C as well.
3.2. Thermal behavior of iron hydrous selenites
A few studies regarding thermal behavior of iron hydrous selenites
with different numbers of water molecules exist in the literature.
Bakeeva et al. (1970) report dehydration of Fe2(SeO3)3∙5H2O at 200 °C.
Rai et al. (1988) examined the thermal behavior of Fe2(SeO3)3∙6H2O
and deduced a two-step dehydration. At 310–350 °C (stage 1) 1.5 mo-
lecules of water are lost and at 350–465 °C (stage 2) 4.5 molecules of
water are lost, with both stages accompanied by partial decomposition
with the release of selenium dioxide. As mentioned above, Giester et al.
(1996) cast doubts on the water content of the ferric selenite hydrate
synthesized by Rai et al. (1988) and clarify that Rai et al. (1988) studied
Fe2(SeO3)3∙3H2O instead of Fe2(SeO3)3∙6H2O. Thus, the scheme of de-
hydration by Rai et al. (1988) is questionable. Giester and Pertlik
(1994) show that the dehydration of Fe2(SeO3)3∙3H2O occurs in two
stages. At the first stage (140 °C) Fe2(SeO3)3∙3H2O loses one molecule of
water and at the second stage (230 °C) the remaining two molecules of
water are lost. Nishimura et al. (2005) describe the thermal behavior of
two crystalline ferric selenite hydrates: Fe2(SeO3)3∙5H2O shows two
steps of weight loss (two-stage dehydration) in the temperature range of
130–180 °C and Fe2(SeO3)3∙3H2O starts its weight loss at 200 °C with an
endothermic peak at 329 °C. In the most recent publications Larrañaga
et al. (2008) determine the dehydration of Fe2(SeO3)3∙3H2O at
200–350 °C.
Representative measurements of thermal behavior of iron hydrous
selenites synthesized in the present study are illustrated in Figs. 3–6.
Fig. 3 – top shows TG, DTG and DSC curves of Fe2(SeO3)3∙3H2O
(sample #6; synthesized at 110 °C, 2.7 bar, 259 days). Two endothermic
effects, which overlap each other, are observed up to a temperature of
∼350 °C, i.e. dehydration of Fe2(SeO3)3∙3H2O seems to occur in two
stages. Within the experimental error the ratio of areas is equal to 2:1
(Fig. 3 – bottom), i.e. 2 molecules H2O are lost at the first stage, and 1
molecule of water is lost at the second stage. The total weight loss
observed within the entire temperature interval up to ∼400 °C
(−9.8 wt.%) is in good agreement with the theoretical weight loss
(−9.9 wt.%) calculated for the dehydration reaction
Fe2(SeO3)3·3H2O → Fe2(SeO3)3 + 3H2O. The theoretical (calculated)
mass loss during the dehydration of various ferric selenite hydrates is
summarized in Table 4. The mass loss of dehydration based on thermal
analysis ranged from −8.7 to −10.0 wt.% in other synthesized samples
of the present study with 3 molecules of water (as derived from XRD
patterns) and the temperature range of dehydration slightly varied from
241 to 257 °C (the beginning of the 1st stage) to 335–342 °С (the end of
the 2nd stage). The decomposition of the remaining Fe2(SeO3)3 of
sample #6 with the release of SeO2 starts immediately after the dehy-
dration and ends at 746 °C. The observed total weight loss (-71.45 wt.
%) is in good agreement with the theoretical weight loss (-70.7 wt.%)

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A. Holzheid et al. Chemie der Erde 78 (2018) 228–240

Fig. 1. Representative XRD patterns of synthesized iron(III) selenite hydrates.

Top: Fe2(SeO3)3·3H2O (sample #6; 110 °C, 2.7 bar, 259 days).
Bottom: synthetic analogue of mandarinoite (sample #9; 30 °C, 1.5 bar, 47 days).
The blue bars depict the theoretical XRD reflexes of Fe2(SeO3)3·3H2O and mandarinoite.

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A. Holzheid et al. Chemie der Erde 78 (2018) 228–240

Table 3
Cell parameters of mandarinoite, synthetic analogues of mandarinoite, and Fe2(SeO3)3·3H2O.

cell mandarinoite mandarinoite synthetic analogue synthetic analogue Fe2(SeO3)3·6H2Oa Fe2(SeO3)3·3H2O Fe2(SeO3)3·3H2O Fe2(SeO3)3·3H2O
parameters Fe2(SeO3)3·4H2O Fe2(SeO3)3·6H2O of mandarinoite of mandarinoite sample #6
sample #9 sample #19
space group P21/c R3c

а, Å 16.78(3) 16.810(4) 16.824(6) 16.783(15) 10.914 9.360(1) 9.361(1) 9.3645(2)

b, Å 7.86(1) 7.880(2) 7.849(3) 7.817(5) 9.352
c, Å 9.96(6) 10.019(2) 10.010(4) 10.000(7) 8.646 20.297(2) 20.276(1) 20.2646(6)
β, 0 98.3(6) 98.26(2) 98.20(2) 98.24(1) 96.52
V, Å3 1313(4) 1308(2) 1298(2) 876.769 1539.98 1538.8(2) 1539.0(1)
reference Dunn et al., 1978 Hawthorne, 1984 this work this work Rai et al., 1988 Giester and Larrañaga et al., this work
Pertlik, 1994 2008

a
Giester et al. (1996) reinvestigated compounds synthesized by the method of Rai et al. (1988) and concluded that the synthetic phases contained only 3 molecules of H2O.

calculated for the reaction Fe2(SeO3)3∙3H2O → Fe2O3 + 3SeO2 + 3H2O.
To ensure that within the lower temperature range only dehydration
occurs without any partial decomposition, the released volatiles were also
detected in some of the measurements. Those DSC measurements con-
firmed two endothermic processes within the lower temperature range
(up to 350 °C) and according to mass spectrometry these processes are
accompanied by release of only water (ion current m/e = 18 – H2O).
Subsequent decomposition of anhydrous iron selenite occurs in the tem-
perature range 358–746 °C and is also accompanied by two endothermic
effects. A sharp exothermic effect on the DSC curve is observed at a
temperature of 473 °C, which obviously corresponds to the phase crys-
tallization of Fe2(SeO3)3. Fig. 4 depicts a representative example of those
TG measurements and DSC data of mass spectrometry of the released
gases, including the ion current value of H2O.
The results of comprehensive thermal analyses applied to the first
synthesized analogue of mandarinoite (sample #9; synthesized at 30 °C,
1.5 bar, 47 days) are illustrated in Fig. 5 – top (TG, DTG, DSC curves).
Please note that the classification of having synthesized an analogue of
mandarinoite is based on XRD and cell parameter calculations. From
Fig. 5 – top it is seen that within the temperature range 25–300 °C, there
are two endothermic effects accompanied by mass losses. These effects
occur in the temperature intervals 84–179 °C and 182–228 °C, respec-
tively. The total mass loss of these two effects is −15.25 wt.%, which
well coincides with the calculated value of mass loss of the dehydration
reaction of ferric selenite hydrates with 5 molecules of water, i.e.
Fe2(SeO3)3·5H2O → Fe2(SeO3)3 + 5H2O (−15.4 wt.%), see Table 4.
Thus, the synthesized ferric selenite hydrate seems to contain five
molecules of water, and not four molecules or six molecules as assumed
by Dunn et al. (1978) and calculated by difference based on electron
microprobe data or by Hawthorne (1984) and derived from single

Fig. 2. Secondary electron images of representative post-run charges.

A–C: Fe2(SeO3)3·3H2O. (A, B: sample #7, C: sample #8; both runs were at 75 °C, 1.5 bar, 27 days).
D, E: Fe2(SeO3)3·3H2O + Fe2(SeO3)3·6H2O. (sample #10; 30 °C, 1.5 bar, 47 days).
F: Fe2(SeO3)3·6H2O. (sample #9; 30 °C, 1.5 bar, 47 days).

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A. Holzheid et al. Chemie der Erde 78 (2018) 228–240

Fig. 3. TG, DTG and DSC curves (top) and peak separation (bottom) of synthesized Fe2(SeO3)3·3H2O.
Sample #6; 110 °C, 2.7 bar, 259 days − heating ramp of thermal analysis: 5 °C/min.
Top figure: TG, DSC, DTG curves.
Bottom figure: experimental data (squares) and result of experimental data approximation (black line), approximations by Fraser-Suzuku function to separate overlapping peaks (gray
lines).

crystal XRD structure solution and refinement, respectively.
The at first glance unexpected result of synthesized
Fe2(SeO3)3·5H2O with cell parameters identical to those derived by
Dunn et al. (1978) and Hawthorne (1984) led us systematically perform
thermal analysis of further synthesized samples of ferric selenite hy-
drates that are all classified as synthetic analogues of mandarinoite
based on XRD. The data obtained show that mass loss during dehy-
dration ranges from −15.3 to −15.7 wt.%, similar to the calculated
mass loss of the reaction Fe2(SeO3)3·5H2O → Fe2(SeO3)3 + 5H2O, but
significantly different to the calculated mass loss values of either
Fe2(SeO3)3·6H2O (−17.9 wt.%) or Fe2(SeO3)3·4H2O (−12.7 wt.%), see
Table 4.
The first effect in dehydration of Fe2(SeO3)3·5H2O within the tem-
perature interval of 84–179 °C (Fig. 5 – top) corresponds to a weight
loss of −9.32 wt.%, implying loss of 3 molecules of water. Within this
narrow temperature interval already two endothermic effects overlap
each other. Peak separation result in a ratio of the areas of 2:1 within
the experimental error (Fig. 5 – bottom).

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A. Holzheid et al.
Fig. 4. TG, DSC and ion current curves of synthesized Fe2(SeO3)3·3H2O.
Sample #5; 110 °C, 2.7 bar, 259 days.
Heating ramp of thermal analysis: 10 °C/min.
Thus, the entire dehydration occurs according to the scheme:
1st stage (temperature interval 84–179 °C) with two dehydration
reactions
Fe2(SeO3)3·5H2O − 2H2O → Fe2(SeO3)3∙3H2O
Fe2(SeO3)3∙3H2O − H2O → Fe2(SeO3)3∙2H2O
2nd stage (temperature interval 182–228 °C) with one dehydration
reaction
Fe2(SeO3)3∙2H2O − 2H2O → Fe2(SeO3)3.
Fig. 5 – top shows not only the mass loss due to dehydration but also
the mass loss due to dissociation at higher temperatures (343–665 °C),
which is accompanied by two endothermic effects. An exothermic effect
is observed on the DSC curve at a temperature of 459 °C, which ob-
viously corresponds to the phase crystallization.
The observed total weight loss (−71.73 wt.%) is in accordance with
the calculated theoretical value of reaction Fe2(SeO3)3∙5H2O →
Fe2O3 + 3SeO2 + 5H2O (−72.6 wt.%).
To ensure that partial loss of water does not occur during storage of
synthesized analogue of mandarinoite, thermal analysis of the sample
#19 (synthesized at 30 °C, 1.5 bar, 61 days) was carried out im-
mediately after completion of its synthesis. The results are presented in
Fig. 6. Fig. 6 – top shows that the total mass loss during dehydration is
−15.36 wt.%, which coincides with the dehydration value for
Fe2(SeO3)3∙5H2O. The dehydration starts at 56 °C and proceeds in two
stages, namely within the temperature ranges of 56–180 °C and
186–226 °C. In contrast to sample #9 discussed earlier, not 3 but 4
water molecules are lost within the first temperature interval (mass loss
is −12.34 wt.%). Based on the dividing peaks method the ratio of the
areas (within the experimental error) equals 1:1 (Fig. 6 – bottom).
The dehydration of sample #19 follows a slightly different scheme:
1st stage (temperature interval 56–180 °C) with two dehydration
reactions
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Chemie der Erde 78 (2018) 228–240
Fe2(SeO3)3·5H2O − 2H2O → Fe2(SeO3)3∙3H2O
Fe2(SeO3)3∙3H2O − 2H2O → Fe2(SeO3)3∙H2O
2nd stage (temperature interval 186–226 °C) with one dehydration
reaction
Fe2(SeO3)3∙H2O − H2O → Fe2(SeO3)3.
In consideration of thermal behavior observations of all synthesized
analogues of mandarinoite of the present study, dehydration most likely
starts at 56–87 °C and ends at 226–237 °C.
To conclude, the most probable formula of synthetic analogues of
mandarinoite seems to be Fe2(SeO3)3∙5H2O in accordance to our find-
ings and in agreement with literature data of Bakeeva et al. (1970) and
Nishimura et al. (2005) for thermal analysis of ferric selenite hydrates.
Different syntheses seem to have diverse ways of dehydration. The
reason remains vague. Two possible schemes of dehydration could be
derived in the present study:
1) in the first stage the sample loses three molecules of water and in the
second stage the remaining two molecules of water;
or
1) in the first stage the sample loses four molecules of water and in the
second stage the last molecule of water.
To complete the study on thermal behavior of synthetic analogues of
mandarinoite, representative syntheses were also studied in situ by High
Temperature X-ray Powder Diffraction. Unit cell parameters at different
temperatures were refined by Topas program (TOPAS v.4.2 by Bruker
AXS – Rietveld full profile refinement software).
Fig. 7 illustrates changes of XRD pattern with temperature of sample
#20. At temperatures above 110 °C the intensity of peaks is
A. Holzheid et al. Chemie der Erde 78 (2018) 228–240

Fig. 5. TG, DTG and DSC curves (top) and peak separation (bottom) of synthesized analogue of mandarinoite.
Sample #9; 30 °C, 1.5 bar, 47 days − heating ramp of thermal analysis: 5 °C/min.
Top figure: TG, DSC, DTG curves.
Bottom figure: experimental data (squares) and result of experimental data approximation (black line), approximations to separate overlapping peaks (gray lines) − 1 st peak: Fraser-
Suzuku function, 2nd peak: Gaussian function.

significantly reduced relative to initial values, indicating that the syn-
thesized substance transformed into amorphous. Already at 100 °C
changes in peaks can be seen as they become less pronounced. The
dependence of unit cell parameters of Fe2(SeO3)3·5H2O as function of
temperature is shown in Fig. 8. A drastic change in the unit cell para-
meters occurs above 80 °C accompanied by lower accuracy of unit cell
parameters’ determination. Insignificant non-linearity of temperature
dependence of unit cell parameters at 60 °C may be caused by the
beginning of dehydration of the sample. This is in accordance with the
observed onset of dehydration at 56 °C based on the DSC results (see
Fig. 6 – top).
Structural analysis performed on a single crystal of mandarinoite
(Hawthorne, 1984) revealed that the crystal structure (Fig. 9a; redrawn
after Hawthorne, 1984) contains three crystallographically non-
equivalent Se4+ atoms, surrounded by O atoms to form a trigonal
pyramid with Se atom in its apical vertex which extends from the base

235
A. Holzheid et al. Chemie der Erde 78 (2018) 228–240

Fig. 6. TG, DTG and DSC curves (top) and peak separation (bottom) of synthesized analogue of mandarinoite.
Sample #19; 30 °C, 1.5 bar, 61 days − heating ramp of thermal analysis: 2 °C/min.
Top figure: TG, DSC, DTG curves.
Bottom figure: experimental data (squares) and result of experimental data approximation (black line), approximations to separate overlapping peaks (gray lines) − 1st peak: Fraser-
Suzuku function, 2nd peak: Gaussian function.

Table 4
Calculated mass loss during the dehydration of ferric selenite hydrates with different
amounts of water.
ferric selenite hydrate
Fe2(SeO3)3·6H2O → Fe2(SeO3)3 + 6H2O
Fe2(SeO3)3·5H2O → Fe2(SeO3)3 + 5H2O
Fe2(SeO3)3·4H2O → Fe2(SeO3)3 + 4H2O
Fe2(SeO3)3·3H2O → Fe2(SeO3)3 + 3H2O
plane of oxygen atoms for 0.80–0.82 Å. There are also two Fe3+ atoms
in the structure of mandarinoite octahedrally coordinated by six O
atoms. Fe(1) cations form 4 bonds with O atoms of selenite pyramids
while another two bonds are slightly elongated and accounted for water
mass loss, % molecules (H2O(10) and H2O(11)). Fe(2) cations form 5 bonds with O
atoms of selenite polyhedra and another one with a H2O(12) molecule.
17.9
15.4 Coordination polyhedra of Se4+ and Fe3+ cations form a vertex-sharing
12.7 framework architecture with large elliptical channels (∼8 × 5 Å) along
9.9 the [001] direction. Structural analysis also showed the presence of

236
A. Holzheid et al.
Fig. 7. Variation of X-ray diffraction pattern of synthesized analogue of mandarinoite (sample #20; 30 °C, 1.5 bar, 61 days) with temperature.
three crystallographically non-equivalent positions of O atoms within
these channels that are attributed to water molecules (H2O(13), H2O
(14) and H2O(15)). Hawthorne (1984) suggested that all available po-
sitions of water molecules are fully occupied and, hence, the formula of
the mineral mandarinoite should be written as Fe2(SeO3)3·6H2O even
despite the fact of high atomic displacement parameters (ADP) of
‘zeolitic’ water molecules (especially for O(14) atom, that are twice
higher than those for O(13) and O(15)). Such high values of ADP could
lead to erroneously assigned full occupancy of those positions. For in-
stance, 0.5 per formula unit (p.f.u.) value for the O(14) atom would
equalize its displacement parameters with O(13) and O(15), and only
this action revises the formula of mandarinoite to Fe2(SeO3)3·5.5H2O.
Taking into account the unique architecture with elliptical channels
in the structure of mandarinoite (Fig. 9a) and evolution of its unit cell
parameters with heating (Fig. 8), the dehydration process could be
described as follows: the release of ‘zeolitic’ water molecules from the
channels causes compression of structure along [010] direction while
the a parameter even increases at the temperature range of 20–60 °C.
Regular increase of the c parameter follows from the dynamics of lattice
to maintain its stability. Subsequent total release of ‘zeolitic’ water
molecules results in a complete desintegration of the channels and re-
arrangement of Se4+ and Fe3+ coordination polyhedra into the more
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Chemie der Erde 78 (2018) 228–240
dense framework of Fe2(SeO3)3·3H2O structure type (Giester and
Pertlik, 1994; as illustrated in Fig. 9b). The possibility of such transition
is also confirmed by the close interatomic distances (a) between the
neighboring Fe atoms within the layer perpendicular to channels in
mandarinoite (Fe(1)-Fe(1) = 5.4 Å) and (b) within (110) plane in the
trihydrate structure (Fe(1)-Fe(2) = 5.6 Å). Further dehydration of ferric
selenite during heating will cause the release of water molecules
bonded to the Fe3+ cations, which in turn results in an increase of
packing density by transition from vertex- to edge-sharing type of
structure formation. According to the thermal analyses, which de-
monstrate the presence of only one water molecule at 180 °C (Fig. 6)
and crystal chemical considerations, the structure of ferric selenite
monohydrate (Giester, 1993; Fig. 9c) with its [Fe2O9(H2O)]12− dimers
is the best candidate for the next structure type in the given phase
transition row present at 180 °C.
4. Conclusions
The data obtained in the present study show that synthetic analo-
gues of mandarinoite neither contain four molecules of water as pro-
posed by Dunn et al. (1978) nor six molecules as suggested by
Hawthorne (1984). The very probable formula of synthetic analogues of
A. Holzheid et al.
Fig. 8. Unit cell dimensions of synthesized analogue of mandarinoite (sample #20; 30 °C, 1.5 bar, 61 days) versus temperature.
mandarinoite seems to be Fe2(SeO3)3∙5H2O. The discrepancy of the
chemical formulas of our synthesized analogues of mandarinoite
(Fe2(SeO3)3∙5H2O) to natural mandarinoite studied by Dunn et al.
(1978; Fe2(SeO3)3∙4H2O) might be due to fact that the water content
was not directly measured by Dunn et al. (1978). The amount of water
was assumed by difference H2O wt.% = 100 wt.% – (Fe2O3 wt.
% + SeO2 wt.%) and the calculated 3.65 molecules of water were
therefore not of high accuracy. Hawthorne (1984) deduced
Fe2(SeO3)3∙6H2O as chemical formula based on only one studied single
crystal of mandarinoite. Hawthorne (1984) neither measured nor ex-
perimentally determined the content of water. The number of water
molecules was derived solely from the structure of the mineral and
inferred from six possible positions for molecules of water in crystal
structure. The structure of mandarinoite as published by Hawthorne
(1984) is shown in Fig. 9a. Hawthorne (1984) linked three molecules of
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Chemie der Erde 78 (2018) 228–240
water in pseudo-octahedral arrangements to the two Fe3+ positions.
The Fe(1) position is coordinated by four oxygen atoms and two mo-
lecules of water, and the Fe(2) position by five oxygen atoms and one
molecule of water. The remaining three molecules of water are not
associated with Fe or Se atoms and are placed in cavities of the struc-
ture. They are only held in the structure by hydrogen bonds (atoms O
(13), O(14) and O(15) in Fig. 9a). Perhaps the behavior of these mo-
lecules determines the characteristics of the processes of dehydration
and the fact that we have observed two possible mechanisms of dehy-
dration for different samples.
The comparison of powder XRD patterns of this study’s synthesized
analogues of mandarinoite with theoretical pattern calculated from the
structural data of Hawthorne (1984) leaves no doubt that the material
in both cases is the same (cf. Fig. 1 – bottom) although the crystallinity
of our synthesized analogue of mandarinoite is not such as superb and
A. Holzheid et al.
Fig. 9. Crystal structures of ferric selenite hydrates: (a) mandarinoite Fe2(SeO3)3·6H2O, (b) Fe2(SeO3)3·3H2O, (c) structure of Fe2(SeO3)3·H2O with clarified [Fe2O9(H2O)]12− dimers.
Fe3+-centered octahedra = blue, Se atoms = orange, O atoms = red,
H atoms = light grey, H-bonds = red dashed lines.
the occupancy of ‘zeolitic’ water molecules might be less than 1.0 p.f.u.
A minor lack of ‘zeolitic’ water molecules in the structure might cause
only a slight change of the crystal structure that could even be not
detectable by XRD. Thus, XRD patterns of synthesized analogues of
mandarinoite and theoretical pattern of mandarinoite as described by
Hawthorne (1984) are indistinguishable.
Based on the XRD measurements and thermal analyses we re-
commend Fe2(SeO3)3·(6-x)H2O, where x = 0.0–1.0, as formula of
mandarinoite. Moreover, the amount of water apparently affects the
crystallinity, and possibly the stability of crystals: the less the x value,
the higher crystallinity could be expected. Such crystal-chemical de-
pendence on the amount of ‘zeolitic’ water was recently discussed and
applied to hydrated calcium oxalates (Izatulina et al., 2014).
Acknowledgments
This study was supported by St. Petersburg State University (grants
numbers 3.38.286.2015 and 3.42.733.2017). The St. Petersburg State
239
Chemie der Erde 78 (2018) 228–240
University Resource Centers “X-ray Diffraction Methods”,
“Thermogravimetric and Calorimetric Research Centre” and
“Geomodel” made their equipment available for this study. The authors
thank Marlene Dreizler, Sebastian Meier, Birgit Mohr, and Maria
Krzhizhanovskaya for help and assistance in performing the experi-
ments, SEM images, and High Temperature X-ray Powder Diffraction.
The paper significantly benefited from the comments of four anon-
ymous reviewers.
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