Mineralogical Magazine, October 2013, Vol. 77(7), pp. 3019–3026

Deveroite-(Ce): a new REE-oxalate from Mount
Cervandone, Devero Valley, Western-Central Alps, Italy
A. GUASTONI1, F. NESTOLA2,*, P. GENTILE3, F. ZORZI2, M. ALVARO2, A. LANZA4, L. PERUZZO5, M. SCHIAZZA6 AND
N. M. CASATI7
1

Museo di Mineralogia, Università di Padova, Via Giotto 1, I-35122, Padova, Italy
Dipartimento di Geoscienze, Università di Padova, Via Gradenigo 6, I-35131, Padova, Italy
3
Dipartimento di Scienze Geologiche e Geotecnologie, Università di Milano-Bicocca, Piazza della Scienza 4,
I- 20100 Milan, Italy
4
Dipartimento di Scienze Chimiche, Universita di Padova, Via Marzolo 1, I-35131 Padova, Italy
5
C.N.R., Istituto di Geoscienze e Georisorse, Via Gradenigo 6, I-35131 Padova, Italy
6
Department of Earth Sciences, University G. d’Annunzio, I-66100 Chieti, Italy
7
Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
2[Received 25 July 2013; Accepted 19 September 2013; Associate Editor: A. Christy]
ABSTRACT

Deveroite-(Ce), ideally Ce2(C2O4)3·10H2O, is a new mineral (IMA 2013-003) found in the alpine
ﬁssures of Mount Cervandone, overlooking the Devero Valley, Piedmont, Italy. It occurs as sprays ofcolourless elongated tabular, acicular prisms only on cervandonite-(Ce). It has a white streak, avitreous lustre, is not ﬂuorescent and has a hardness of 2–2.5 (Mohs’ scale). The tenacity is brittle andthe crystals have a perfect cleavage along {010}. The calculated density is 2.352 g/cm3. Deveroite-(Ce)is biaxial ( ) with 2V of ~77º, is not pleochroic and the extinction angle (b ^ c) is ~27º. No twinningwas observed. Electron microprobe analyses gave the following chemical formula:(Ce 1.01 Nd 0.33 La 0.32 Pr 0.11 Y 0.11 Sm 0.01 Pb 0.04 U 0.03 Th 0.01 Ca 0.04 ) 2.01 (C 2 O 4 ) 2.99 ·9.99H 2 O. Althoughsynchrotron radiation was not used to solve the structure of deveroite-(Ce) the extremely small sizeof the sample (13 mm63 mm61 mm) did not allow us to obtain reliable structural data. However, it
was possible to determine the space group (monoclinic, P21/c) and the unit-cell parameters, which are:a = 11.240(8) Å, b = 9.635(11) Å, c = 10.339(12) Å, b = 114.41(10)º, V = 1019.6 Å3. The strongest
lines in the powder diffraction pattern [d in Å(I)(hkl)] are: 10.266(100)(100); 4.816(35.26)(211̄);3.415(27.83)(300); 5.125(24.70)(200); and 4.988(22.98)(111). Deveroite-(Ce) is named in recognitionof Devero valley and Devero Natural Park.
K EY WORDS : Deveroite-(Ce), new mineral, oxalate, Devero.

Introduction
MOUNT Cervandone (also named Cherbadung)
overlooks the Devero Valley on the Italian sideand the Wanni Glacier on the Swiss side. It hosts
mineral deposits which are among the mostrenowned in the Lepontine Alps. Six new REEarsenates and REE-arsenites including asbecasite* E-mail: fabrizio.nestola@unipd.it
DOI: 10.1180/minmag.2013.077.7.11# 2013 The Mineralogical Society(Graeser, 1966), cafarsite (Graeser, 1966), cervandonite-(Ce) (Armbruster et al., 1988), fetiasite(Graeser et al., 1994), gasparite-(Ce) (Graeser and
Schwander, 1987) and paraniite-(Y) (Demartin etal., 1994) were ﬁrst described in these localities.
Arsenates, sulfates and vanadates representing ﬁrst
occurrences at Wannigletscherand at Mount
Cervandone were described also by Guastoni etal. (2006), and the crystal-chemistry of an arsenicrich fergusonite-beta-(Y) was ﬁrst characterizedfrom a sample found at Mount Cervandone(Guastoni et al., 2010).

A. GUASTONI ET AL.

In this study we describe a new mineral named
deveroite-(Ce), ideally Ce2(C2O4)3·10H2O, foundat Mount Cervandone, Devero valley, WesternCentral Alps, Italy. Deveroite-(Ce) was ﬁrst
identiﬁed in 2008 by Enzo Sartori and Vittorio
Soldani, local collectors who collaborated with
one of the authors (A.G.) and the Parco VegliaDevero on the project of studying the mineralogyof Mount Cervandone.
Deveroite-(Ce) is the third natural oxalate
found in the alpine ﬁssures of Mount
Cervandone after moolooite, Cu(C2O4)·nH2O(Guastoni, 2009) and lindbergite,
Mn 2+ (C 2 O 4 )·2H 2 O (Albertini and Meisser,2012). These minerals occur in Alpine ﬁssures,
crystallized by circulation of meteoric waters
enriched with oxalic acid, similar to themechanism reported by Krzemnicki (1996) for
the formation of wheddellite in the Binntal region.
Despite the crystals being extremely thin andsmall (crystal sizes, 450 mm65 mm65 mm), a
combined single-crystal and powder X-ray
diffraction (XRD) analysis allowed determinationof space group and unit-cell parameters fordeveroite-(Ce) which, together with the microprobe analysis, highlighted the crystal-chemical
relations with its synthetic analogues Ce-oxalate,
La-oxalate and Nd-oxalate.
Deveroite-(Ce) was approved by the IMACommission on New Minerals, Nomenclature andClassiﬁcation (CNMNC) IMA2013-003. The
mineral is named in recognition of the Devero
valley and the Devero Natural Park where, for the
past several years, a research project has been
carried out and promoted by the Museum ofMineralogy of the University of Padova to study
the mineralogy of this area of the Italian Alps.
The holotype material is deposited in themineralogical collection of the Museum ofMineralogy of the Department of Geosciences at
the University of Padova (Italy), under catalogue
number MMP M12148.
Occurrence
The area of Mount Cervandone includes steep
rock walls and a talus ﬁeld between the‘Bandiera’ peak and ‘Canalino Ferrari’. This
area is characterized by swarms of sub-horizontal
and parallel ‘white’ dykes with pegmatitic
texture, which crop out for several metres along
the central body of Mount Cervandone. Thesepegmatitic dykes, which cross cut the metamorphic rocks, are hosted by very ﬁne-grained
3020

two-mica leucocratic gneisses belonging to the‘Mount Leone-Arbola’ nappe (Dal Piaz, 1975).
These dykes are tens of centimetres thick, andtens of metres long, and are composed of coarse
vitreous quartz, K-feldspar and greenish micas.
Sporadic pegmatitic dykes contain fractured black
tourmaline prisms and contorted mica ﬂakes
embedded in vitreous ‘smoky’ quartz, andexhibit boudinage-like textures. Locally thepegmatite dykes are cross cut by metre-longquartz veins up to several decimetres thick. The
quartz veins are usually subvertical and discordant with respect to the foliation of the gneiss hostrock and contain open ﬁssures lined with quartz
crystals, frequently containing Be-As-Y-REE
minerals. In the pegmatite dykes, the Be, As, Y
and REE minerals occur more frequently than in
the quartz veins. The pegmatites show a strong
NYF (niobium, yttrium, ﬂuorine) geochemicalsignature, represented by the occurrence of aunique mineralogy that includes: aeschynite-(Y),agardite-(Y), Nb-rich anatase, arsenic-richfergusonite-beta-(Y), cervandonite-(Ce), chernovite-(Y), crichtonite-senaite, ﬂuorite, gadolinite(Y), monazite-(Ce), paraniite-(Y), synchysite(Ce), and xenotime-(Y) (Graeser and Stalder,
1976; Albertini, 1991; Graeser and Albertini,1995).
It is evident that the formation of deveroite(Ce) requires a source of oxalate, a source ofREEs, and the presence of water as the ﬂuid
medium allowing REE and oxalate ions to form
soluble REE-oxalate complexes (Gammons andWood, 2000). A source of oxalate is provided byincomplete oxidation of organic material, such as
decaying plant remains. In this case it is more
likely that the source was crusty lichens, such as
Lecidea geographica, which can survive ataltitudes above 2500 m and is widespread at
Mount Cervandone. Several examples of oxalaterich minerals formed by lichens and fungi arereported in the literature: e.g. Russ et al. (1996)
reported the formation of whewellite, a hydrated
calcium oxalate, on limestones, whilst Chisholm
et al. (1987) described the occurrence of
whewellite and moolooite, a hydrated copper
oxalate, within the medulla of four lichen species
growing on copper bearing rocks. A source of
REE is clearly provided by the hosting mineral,
cervandonite-(Ce), an arsenosilicate with theformula (Ce,Nd,La)(Fe 3 + ,Fe 2 + ,Ti 4 + ,Al) 3 O 2(Si 2 O 7 ) 1 x (AsO 3 ) 1+x (OH) 3x , (Demartin andGramaccioli, 2008). Deveroite-(Ce) occurs only
on crystals of cervandonite-(Ce). The partial

DEVEROITE-(CE): A NEW REE-OXALATE

dissolution of cervandonite-(Ce) by reaction withaggressive meteoric waters enriched with oxalic
acid (HC2O4 )-liberated LREE and allowed theformation of deveroite-(Ce).
Physical and optical properties
Deveroite-(Ce) occurs as sprays of colourless,elongated, tabular or acicular prisms (Figs 1, 2, 3)
only on cervandonite-(Ce). The mineral exhibits
euhedral morphology and shows no inclusions of,or intergrowths with, other minerals. The maximum
size available of single crystals suitable for singlecrystal study was 15 mm. However, scanningelectron microscope images show that deveroite(Ce) can reach a maximum size of ~50 mm.
Deveroite-(Ce) is associated with agardite(Ce), asbecasite, cafarsite, K-feldspar, muscovite,
quartz. It has a white streak, a vitreous lustre, is
not ﬂuorescent, and neither pleochroism nor
twinning was observed. Due to the extremely
limited thickness of the crystals, any possible
attempt at micro-indentation on such thin crystals
could only provide unreliable data. The tenacity isbrittle and the crystals have a perfect cleavage
along {010}. Due to the small grain size, it was
impossible to measure the density, therefore we
report only the value of 2.352 g/cm3 calculatedusing the empirical formula and single-crystal
unit-cell data. Optically, deveroite-(Ce) is biaxial( ). Due to the crystal size of deveroite-(Ce), it
was impossible to obtain the refractive indexes forthe new mineral. However, we report thoseavailable for synthetic La 2 (C 2 O 4 ) 3 ·10H 2 O

FIG. 1. Holotype of deveroite-(Ce): platy, acicular,
prismatic, colourless crystals of deveroite-(Ce) on a
black aggregate of cervandonite-(Ce). The ﬁeld of viewis 1.35 mm wide.

FIG. 2. Backscattered SEM image of the holotype ofdeveroite-(Ce) showing the morphology of the crystal
aggregates.

oxalate, which are: a = 1.473, b = 1.548, andg = 1.601. These refractive indexes should bevery similar to those of deveroite-(Ce), based on
the similarity found for the other optical properties: (1) the measured extinction angle b ^ c is 27ºin the direction +a for deveroite-(Ce), practically
identical to the 26.5º angle for synthetic
La2(C2O4)3·10H2O (Fig. 4); (2) the 2V (77º) is

FIG. 3. Extremely thin and small crystals of deveroite(Ce) from the holotype (top of the ﬁgure). The crystal
was used to obtain the optical properties and the singlecrystal data by synchrotron radiation

3021

A. GUASTONI ET AL.

and UM. The crystal fragment was found to behomogeneous within analytical error. Na, K, Gd,
Tb, Dy, Ho, Er, Tm and Yb were below thedetection limit (of 0.1 wt.%). The mean analyticalresults (11 analyses) are given in Table 1. The
empirical formula (based on 22 O atoms per
formula unit (a.p.f.u.)) obtained from the EMPA
analyses is (with H2O and C2O3 calculated bystoichiometry): (Ce 1.01Nd 0.33La 0.32Pr0.11 Y 0.11
Sm0.01Pb0.04U0.03Th0.01Ca0.04)2.01(C 2 O 4 ) 2.99 ·9.99H 2 O. The ideal formula isCe2(C2O4)3·10H2O, which requires Ce2O3 45.35,
C2O3 29.80, H2O 24.85, total 100.00 wt.%.

identical to that of La2(C2O4)3·10H2O. The
Gladstone-Dale compatibility using the calculated
density is rated as superior.
Experimental methods
Electron microprobe analysis
Microprobe analyses (EMPA) were performed on
the crystal fragment used for the synchrotron
radiation measurement at the Dipartimento di
Scienze Geologiche e Geotecnologie, Università
di Milano-Bicocca. The chemical composition
was determined using a SEM Tescan VEGA TS
5136 XM equipped with energy-dispersive
analysis (EDS) by means of a standardized
EDAX GENESIS 4000 XMS electron microprobe. Major and minor elements were determined at 20 kV accelerating voltage and 190 pA(in a Faraday cup), spot size 250 nm, 100 s as
counting time, and working distance 23 mm. For
the EDS analyses the following lines were used:
CaK, LaL, CeL, PrL, NdL, YL, SmM, PbM, ThM

X-ray diffraction
A single crystal of deveroite-(Ce) 13 mm6
3 mm61 mm in size was analysed by XRD at
Diamond Light Source Ltd. in the extremeconditions beamline (I15). The experiment was
performed using a fully focused beam of l =0.20675 Å, as calibrated by diffraction from a

FIG. 4. Comparison between deveroite-(Ce) and La-oxalate [La2(C2O4)3·10H2O] (Gilpin and McCrone, 1952) inorder to show their similar optical properties. The image of deveroite-(Ce) on the left is an insert from Fig. 3,
whereas on the right side we show part of a drawing from ﬁg. 1 of Gilpin and McCrone (1952) relative to thesynthetic La2(C2O4)3·10H2O oxalate.

3022

DEVEROITE-(CE): A NEW REE-OXALATETABLE 1. Chemical data for deveroite-(Ce).
Constituent

Wt.%

Range

SD

Probe standard

CaO
C2O3*
Y2O3
La2O3
Ce2O3
Pr2O3
Nd2O3
Sm2O3
PbO2
ThO2
UO2
H2O*
Total

0.34
29.7
1.66
7.29
22.8
2.53
7.53
0.24
1.24
0.29
1.05
24.8
99.47

0.25–0.44

0.06

Almandine garnet

1.19–2.04
6.60–8.40
22.03–24.28
2.10–2.88
7.14–7.90
0.13–0.43
1.42–2.53
0.22–0.35
0.86–1.19

0.33
0.53
0.81
0.23
0.29
0.09
0.17
0.04
0.11

Yttrium garnet
Monazite-(Ce)Monazite-(Ce)Monazite-(Ce)Monazite-(Ce)Monazite-(Ce)GalenaUraninite
Uraninite* Calculated from stoichiometry.

NIST ruby sphere. A 20 mm circular pinholedeﬁned the beam size and shape. The crystal was
mounted with a MiTeGen micro-loop on thediffractometer, data were then collected with an
Atlas CCD detector (Agilent technologies) scanning j and o with a width of 1º. The j scan was
performed in the range from –60º to +120º at ak = 137.75º, o = 56º while the o scan was
performed from 15 to 95º at j = 98.00º and k =134.75º. Data were then treated with the
Crysalis software package. Although the extremely small size of the sample did not allow us toreﬁne the structural data, it was possible to obtainthe unit-cell parameters a = 11.240(8) Å, b =9.635(11) Å, c = 10.339(12) Å, b = 114.41(10)º,V = 1019.6 Å3 and the space group was assigned
as monoclinic P21/c based on the systematicabsences.
In order to conﬁrm our results further, X-ray
powder diffraction (XRPD) measurement was
performed on a number of (15 20) crystals. The
XRPD data were recorded on a PANalytical y-ydiffractometer equipped with long ﬁne focus Cu
X-ray tube operating at 40 kV and 40 mA,
focusing crystal mirror (W/Si), capillary spinnerand a solid state detector (PIXCel). The detector
active length (aperture) is 3.347º, and this enables
signal collection over a large angular range at thesame time, reducing the total time of the scan.
The scan was performed over the range 5 70º2ywith an integrated step size of 0.026º2y and a total
time for data acquisition of ~68 h (angular speed
0.00028º/s). This corresponds to a scan with avirtual counting statistic of 24000 s/step. The
program High Score Plus (PANalytical) was used
for phase identiﬁcation and to perform Le Bailstructureless whole-pattern ﬁtting (Le Bail et al.,1988). A pseudo-Voigt function was employed
for the proﬁle shapes. Reﬁned parameters werescale zero-shift, background, lattice constants, andproﬁle parameters (Gaussian and Lorentzian
coefﬁcients). The Le Bail ﬁt gave the following
agreement indices: Rp = 12.39%, Rwp = 15.40%
and RBragg = 5.48%. The list of d spacings
obtained by XRPD for deveroite-(Ce) from the Le
Bail reﬁnement are reported together with theobserved data from simple proﬁle ﬁtting in
Table 2. The unit-cell parameters obtained by
XRPD reﬁnement are: a = 11.2725(9) Å, b =9.6109(9) Å, c = 10.346(1) Å, b = 114.539(7)º,
V = 1019.621 Å3. The unit-cell data from powder
diffraction are in perfect agreement with thoseobtained by single-crystal XRD.
Results and discussion

3023

The ﬁrst attempt to identify deveroite-(Ce) bypowder XRD failed, as we realized that the newmineral did not have any natural analogue.
Extending the search to the synthetic crystalline
compounds, we found a good match of spacegroup symmetry and unit-cell parameters between
deveroite-(Ce) and three synthetic analogues:
Ce2(C2O4)3(H2O)6·4H2O and the isostructural
Nd2(C2O4)3·10H2O (Ollendorff et al., 1969), andLa2(C2O4)3(H2O)6·4H2O (Gilpin and McCrone,

A. GUASTONI ET AL.

TABLE 2. List of d spacings obtained by XRPD
for deveroite-(Ce).
h k ldcalc (Å)

Irel

1 0 0
1 1 0
0 1 1̄
1 1 1̄
1 0 2̄
2 0 0
1 1 1
2 1 1̄
0 2 0
0 0 2
2 1 0
1 2 0
3 0 2̄
1 2 2̄
3 0 0
2 2 2̄
3 1 0
1 3 0
0 3 1̄
2 2 1
0 1 3
2 0 2
3 1 3̄
3 2 0
3 1 1
4 1 1̄
2 3 2̄
1 1 3
2 2 2
4 2 3̄
1 2 4̄
2 1 3
4 1 1
0 4 2̄
4 2 4̄
3 3 4̄
5 2 0
1 4 3
5 3 4̄
7 2 3̄

10.25437.01246.72436.59105.16705.12724.98554.82564.80544.70574.52374.35133.55543.51883.4181
3.29553.2205
3.05793.03273.01722.98232.91572.87102.78542.73662.67402.61532.60142.49282.27162.24152.2243
2.18892.13992.0481
1.95971.8863
1.79561.70581.5247

100
8
8
22
11
29
40
41
42
2
9
7
3
6
27
3
4
10
2
5
4
4
4
5
14
10
6
6
4
2
4
8
7
2
17
3
4
3
2
2

FIG. 5. Unit-cell volume of synthetic oxalates anddeveroite-(Ce) vs. the average ionic radius of the 9-foldcoordinated cations.

idea that, assuming constant volume for both the(C2O4) and H2O groups, the unit-cell volume forthese oxalates is controlled by the size of the
9-fold coordinated cations (i.e. Ce, Nd, La) only.
However, given that structural data are alsolacking for the synthetic compounds, the detailsof the structural role of H2O and its effect onoverall volume cannot be unravelled.
Conclusions

1952; Huang et al., 1991) (Table 3) withanalogous stoichiometries but different 9-foldcoordinated cations. The close structural relationship with these phases is conﬁrmed by the
relationship between unit-cell volume and composition. As shown in Fig. 5, the change incomposition, represented in terms of ionicradius, is signiﬁcantly related to the increase in
the unit-cell volume. This is consistent with the3024

Deveroite-(Ce) is the natural hydrated REEbearing analogue of the La, Ce and Nd synthetic
oxalate compounds. It is likely that it formed bycirculation of meteoric waters at low temperatures, between 20 and 30ºC, temperatures that
occur during the summer at the altitude of thetype locality in the Italian Alps. Further naturalsulfate-oxalates of the REE, coskrenite-(Ce)(Peacor et al., 1999) levinsonite-(Y) and zughunstite-(Ce) (Rouse et al., 2001), seem to be formed
under the same conditions.
With respect to the other two oxalates found at
Mount Cervandone, moolooite and lindbergite,
deveroite-(Ce) seems to be more stable.
Lindbergite, monoclinic Mn(C2O4)·2H2O, isitself a secondary phase that is formed by rapid
dehydration on exposure of the very unstable,
unnamed orthorhombic Mn(C2O4)·2H2O (Atencio
et al., 2004).
Given the organic anion, large water content
and probable thermal instability of deveroite-(Ce),there is unlikely to be any direct genetic
relationship with Alpine hydrothermal ﬂuids.
Deveroite-(Ce) is likely to have formed very

DEVEROITE-(CE): A NEW REE-OXALATETABLE 3. Selected crystallographic data for synthetic REE oxalates.

FormulaDeveroite-(Ce)Ce2(C2O4)3·10H2O

Ce-oxalate (synthetic)[Ce2(C2O4)3(H2O)6]·4H2O

La-oxalate (synthetic)[La2(C2O4)3(H2O)6]·4H2O

Nd-oxalate (synthetic)
Nd2(C2O4)3·10H2O

Cell dataa (Å)b (Å)c (Å)b (º)
V (Å3)

11.2725(9)9.6109(9)10.346(1)114.539(7)1019.64

11.3479.630
10.392114.521033.14

11.382(6)9.624(5)10.502(8)114.52(4)1046.65

11.192
9.612
10.257114.421004.71

SystemSpace group
References

Monoclinic
P21/cThis study

Monoclinic
P21/c
Ollendorf et al. (1969)

Monoclinic
P21/c
Huang et al. (1991)

Monoclinic
P21/c
Ollendorf et al. (1969)

recently at near-surface conditions, from LREE
released by very local dissolution of cervandonite-(Ce), which have been chelated and transported as oxalate complexes (Hofmann andBernasconi, 1998; Gammons and Wood, 2000).
The oxalate, in turn, is probably derived fromorganic material such as lichens.
Acknowledgements
The authors thank Domenico Forloni who donatedthe specimen shown in Fig. 1 used to obtain all
the relevant data of this study and Enrico
Bonacina who photographed the specimen. The
work was supported by ‘‘Progetto d’Ateneo ofUniversity of Padova’’ to FN. The Principal
Editor, Peter Williams, an anonymous referee
and Stuart Mills are thanked for their helpfulcomments, which improved the manuscript.
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