Mineralogy and Petrology (1997) 60:121-132

Mineralogy
an(1
Petrology
Springer-Verlag 1997
Printed in Austria

Ternesite, Ca5(SiO4)2SO4, a new mineral

from the Ettringer Bellerberg/Eifel, Germany
E. Irran 1,*, E. Tillmanns 1, and G. Hentschel 2

1 Institut fiir Mineralogie und Kristallographie, Universitat Wien, Austria

2 Sinzig, Federal Republic of Germany

With 1 Figure

Received February 12, 1997;

accepted April 14, 1997

Summary
The new mineral ternesite, Ca5(SiO4)2SO4, has been found at the Ettringer Bellerberg
near Mayen, Eifel, Germany. The crystal structure, already known from the synthetic
analogue, was refined from single crystal X-ray data: orthorhombic, space group Pnma
with a= 6.863(1)A, b=15.387(2)A, c=10.181(1)A, Z=4, R=0.058, Rw=0.046 for
820 unique reflections with F0> 3o-(F0) and 96 variable parameters. The strongest peaks
in the powder pattern are (d-value (A), I, hkl): 2.830, 100, (033)/2.853, 63, (230)/2.565,
55, (060)/3.198, 42, (132)/1.892, 39, (035) + (125). The mineral is optically biaxial
negative with refractive indices n = 1.630(1) (parallel [100]), ny = 1.637(2) (parallel
[001]), and nz = 1.640(1) (parallel [010]). The optical angle 2Vx was measured as
63.5(5)

Zusammenfassung
Ternesit, Ca5(Si04)2S04, ein neues Mineral vom Ettringer Bellerberg, Eifel, Deutsch-
land
Das neue Mineral Ternesit, Ca5(SiO4)2SO4, wurde am Ettringer Bellerberg bei Mayen,
Eifel, Deutschland gefunden. Die schon vom synthetischen Analogen her bekannte
Kristallstruktur wurde aus Einkristalldaten yon nattirlichem Material verfeinert: Das
Mineral ist orthorhombisch, Raumgruppe Pnma mit a= 6.863(1)A, b=15.387(2)A,

* Present address: Laboratorium ftir Anorganische Chemie I, Universit~it Bayreuth,

Federal Republic of Germany
122 E. Irran et al.

c=10.181(1)A, Z=4, R=0.058, Rw=0.046 ftir 820 unabh~ngige Reflexe mit

Fo> 3cr(Fo) und 96 variablen Parametern. Die st~rksten Maxima im Pulverbeugungs-
diagramm sind (d-Wert (A), I, hkl): 2.830, 100, (033)/2.853, 63, (230)/2.565, 55, (060)/
3.198, 42, (132)/1.892, 39, (035) + (125). Das Mineral ist optisch zweiachsig negativ
mit Brechungsindizes n : 1.630(1) (parallel [100]), ny : 1.637 (2) (parallel [001]),
und nz : 1.640(1) (parallel [010]). Der optische Achsenwinkel 2Vx wurde zu 63.5(5)
gemessen.

Introduction
Recently, two Ca-rich xenoliths containing an unknown light blue mineral were
found at the Ettringer Bellerberg near Mayen (Eifel/Germany) by Mr. B. Terries
(Mayen). The X-ray diffraction pattern of the blue mineral resembles that of
synthetic Cas(NiO4)2SO 4 (PDF 26-1071) which is known as the main component of
the green sulphate rings accumulating in cement rotary kilns. This phase is isotypic
to Cas(PO4)2SiO4 ('silicocarnotite') and to some other Ca or Cd containing
compounds.
The mineral was named after Mr. Ternes, who not only found the mineral and
provided samples for this investigation but also contributed a lot to our knowledge
of the minerals of the Eifel area. Mineral and mineral name have been approved by
the IMA Commission on New Minerals and Mineral Names prior to publication
(# 95-015). Type material is deposited at the Institut ftir Mineralogie und Kristal-
lographie, Universit~it Wien and at the Naturhistorisches Museum, Wien, Austria.

Occurrence and paragenesis

The Ettringer Bellerberg volcano is part of the Laacher See area in the Eastern
Eifel which was active in the Quaternary (Frechen, 1976). Its leucite tephrite lava
contains many inclusions of different kinds of rock altered by high-grade thermo-
metamorphism. Of special interest are the Ca-rich xenoliths, to which the rocks
containing ternesite belong, because of their unusual paragenesis of rare minerals
(Jasmund and Hentschel, 1964).
The analysis of the host rock by powder diffraction patterns and by optical
examination of a thin section showed that it consists mainly of ternesite, ellestadite
and a solid solution between ettringite and thaumasite. In addition other calcium
silicates like mayenite, tobermorite, calcio-olivine, and larnite, also portlandite,
magnetite, and hematite were detected.
The Ca-rich xenoliths found at the Bellerberg are possibly marly limestone
incorporated into the leucite tephrite lava and decarbonized at high temperatures
(Jasmund and Hentschel, 1964). This high temperature paragenesis is represented
by mayenite, known as the phase C12A7 of tile cement clinker, by larnite, which is
restricted to the hornfels facies (Turner, 1981), and by brownmillerite. As ternesite
is the only water-free sulphur-containing component of the xenoliths, it can be
supposed that it also belongs to the high temperature paragenesis. Ellestadite and
ettringite/thaumasite were formed by subsequent hydratization at lower tempera-
tures. Additional alteration products of the original paragenesis are tobermorite,
portlandite, and calcio-olivine.
 A new mineral from the Ettringer Bellerberg/Eifel 123

Synthetic Ca5(SiO4)2SO4
Ca5(SiO4)2SO 4 was described for the first time by Sundius and Peterson (1960) as
the colouring component of the green sulphate rings in cement rotary Kilns. It is
one of the complex sulphates formed in the Mueller-Kuehne process where CaSO4
is used as Ca supplier instead of CaCO3 (Smith and Gutt, 1971). These complex
sulphates subsequently decompose to the essential clinker minerals Ca3SiOs,
CazSiO4, and Ca3A1206. Pryce (1972) describes crystals of Ca5(SiO4)2SO4 from
lime kiln wall coating where the kiln feed was calcite and quartz. Here the sulphur
necessary for the formation of Ca5(SiO4)2SO4 was supplied by the fuel which was
an oil with a high sulphur content. Experiments performed by Gutt and Smith
(1966, 1967) showed that Ca5(SiO4)2SO4 is formed at temperatures of about
1000C and decomposes at 1150C in an open system and at about 1300C in
closed platinum crucibles. For the reaction CaSO4 + 2Ca2SiO4-=-Ca5(SiO4)2SO4
an activation energy of (157 :k 3) kJ/mol was derived (Hanic et al., 1986).
Natural ternesite therefore should be formed between 1000 and 1300 C at low
pressure, which is consistent with the conditions found for the paragenesis of the
xenoliths. Sulphur theoretically can be supplied by sulphates in the original rock or
by sulphur containing gases from the host rock. As stated by Jasmund and
Hentschel (1964) the Ca-rich xenoliths from the Ettringer Bellerberg seem to
receive the sulphur from the sulphur rich gases of the magmatic host rock.

Physical properties and chemical composition

Ternesite forms aggregates of radially arranged prismatic crystals elongated along
[100]. Their size is up to 0.2 mm in length and about 0.05 mm in diameter. The
crystals show no cleavage, the Moh's hardness is 4.5 to 5. The density determined
by mixing of heavy liquids under the microscope is 2.94(2) Mg/m 3, the calculated
density is 2.97 Mg/m 3. The colour is bright blue only in aggregates, single crystals
are colourless. No fluorescence was observed.
The optical constants of ternesite were determined on a spindle stage using
light with a wavelength of 586 nm. The mineral is optically biaxial negative with
refractive indices nx = 1.630(1) (parallel [100]), ny -- 1.637(2) (parallel [001]), and
nz = 1.640(1) (parallel [010]). The optical angle 2Vx was measured as 63.5(5) , the
theoretical angle calculated from the refractive indices gives 66(5) . The optical
constant of Ca5(8iO4)2SO 4 from a lime kiln determined by Pryce (1972) are nx =
1.632(1), ny = 1.638(1), nz = 1.640(1) and 2Vx = 60(1) , which agrees well with
the constants of the natural sample.
The chemical composition was determined by EDX measurement on a JEOL
JSM-6400 scanning electron microscope (operating voltage 20 kV, channel width
20 eV). The standards were wollastonite for CaO and SiO2 and anhydrite from
Stassfurt/Germany for SO3. The measured data were corrected for attenuation
effects by the program system LINK exL10 (Link Analytical Ltd., B u c k s ,
England). Table 1 shows the range and average chemical composition obtained
from seven analyses and the theoretical composition of Ca5(SiO4)2SO4. On the
basis of 12 oxygen atoms the empirical chemical formula was calculated as
Ca5.04Si2.01S0.98012, idealised Ca5(SiO4)2SO 4.
124 E. Irran et al.

Table 1. Chemical composition of ternesite (in weigth percent)

Range Average Standarddeviation Theoretical
CaO 57.32-60.35 58.90 0.83 58.34
SiQ 23.05-27.23 25.22 1.28 25.00
SO3 13.80-18.04 16.34 1.25 16.66
Z=100.46 Z=100.00

As none of the major element seems to be responsible for the bright blue
colour of ternesite, a XRF analysis was performed to look for traces of transition
elements which could not be detected by the EDX measurements. The analysis was
carried out on a PHILIPS PW2400 X-ray spectrometer with Rh-anode, 3 kW
generator and LiF(200) analysator (voltage 60 kW, current 50 mA). Traces of iron
and titanium were found, but due to the small sample no quantitative analyses
could be performed. As it is supposed to be the cause of the blue colour of sapphire
and cyanite (Nassau, 1978), ternesite is likely coloured by a charge transfer be-
tween Fe 3+ and Ti 4+. In contrast synthetic Ca5(SiO4)2SO 4 usually is green, the
chemical analysis of Ca5(SiO4)2SO4 synthesised from high purity Ca2SiO4 and
CaSO4 by Gutt and Smith (1966) showed a FeO-content of 0. l weight%. Samples
of Ca5(SiO4)2SO4 from lime kiln wall coating analysed by Pryce (1972) showed a
high Fe203- (0.5 weight%) and FeO- content (100 ppm), but only 50 ppm TiO2 and
similar amounts of other metallic oxides. Therefore it can be assumed that the
green colour of synthetic Ca5(SiO4)2SO4 is caused only by iron ions.
The agreement between measured density, refractive indices and chemical
composition was checked by the Gladstone-Dale relationship using the constants of
Mandarino (1976). The compatibility index (1-kp/kc) after Mandarino (1981) gives
-0.054, which falls into the category "good".

X-ray investigations
A portion of ternesite was ground, fixed on a fiat cut silicon single crystal sample
holder, and measured with a Philips PW3020 X-ray diffractometer. The peak po-
sitions were corrected with silicon as internal standard, and the program NBS*-
AIDS80 (Mighell et al., 1983) was used to index the powder diffraction pattern and
refine the lattice constants of the orthorhombic cell (a = 6.863(1) A, b = 15.387(2)
A, c = 10.181 (1) *). A detailed powder pattern has been deposited for the Powder
Diffraction File with JCPDS/ICDD, it is also available from the authors upon
request. The strongest peaks in the powder pattern are (d-value (A), I, hkl): 2.830,
100, (033)/2.853, 63, (230)/2.565, 55, (060)/3.198, 42, (132)/1.892, 39, (035) +
(125). The powder diffraction pattern of ternesite shows good agreement with
synthetic Ca5(8iO4)2SO 4 (PDF 26-1071), although the highest peaks differ some-
what in intensity because of a preferred orientation of the natural sample due to the
elongation of its crystallites parallel [100].
A crystal large enough for single crystal diffraction was chosen by oscillation
photographs, and was used for data collection on a STOE AED2 automatic four
 A new mineral from the Ettringer Bellerberg/Eifel 125

Table 2. Summary of crystal data, X-lay measurement and structure refinement of

ternesite
Formula Ca5(SiO4)2SO4
Molecular weight 480.62
Space group Pnma (No. 62)
Formula units per cell 4
a[,~] 6.863(1)
b[]~] 15.387(2)
c[A] 10.181(1)
Volume [~3] 1075.1
Calculated density [Mg/m3] 2.968
Crystal size [mm3] 0.054 x 0.090 x 0.179
Range of data collection [20] 3-55
Steps per peak 35
Step width [20] 0.03
Background measurement 2 x 5 steps
Measuring time per step [s] 1-3
Measured reflections 2732
Unique data set 1231
Data with F0 > 3(F0) 820
F(000) 960.0
Rint 0.0600
R 0.0582
Rw 0.0459

circle diffractometer. The lattice constants were determined by exact measurements

of the positions of nine reflections and their symmetrically equivalent ones, they
were in good agreement with the more accurate constants derived from the powder
data. The measured intensities were corrected for Lorentz and polarisation effects
as well as for absorption by empirical ~-scans. The non-extinction rules are
consistent with the possible space groups Pn21a and Pnma, the latter was confirmed
by the crystal structure refinement. Table 2 gives some details of the crystal data
and the refinement procedure.
For refinement the program SHELX76 (Sheldrick, 1976) was used, the atomic
scattering factors were taken from the International Tables of Crystallography,
Vol. C (Wilson, 1992), the anomalous scattering factors from the International
Tables for X-ray Crystallography, Vol. IV (Ibers and Hamilton, 1974) and the
absorption coefficients from Vol. II (Kasper and Lonsdale, 1956). The atomic
coordinates of Cas(PO4)2SiO4 ('silicocarnotite') given by Dickens and Brown
(1971) were used as starting model of the structure refinement. At the beginning
the sulphur atoms were placed on the tetrahedra T(1)O4 on the mirror plane
(Wyckoff position 4c) and silicon on the tetrahedra T(2)O4 in general position
(Wyckoff position 8d) in contrast to Cas(PO4)2SiO4 which shows a more compli-
cated distribution of the cations over the two tetrahedral position. During the
refinement the cation-oxygen distances of the tetrahedra did not contradict this
distribution, so it was kept till the end of the refinement. The refinement converged
at a residual of 0.058 and a weighted residual of 0.046. A final difference Fourier
126 E. Irran et al.

Table 3. Atomic coordinates and equivalent isotropic displacement factors

(~2). For the definition of Beq see Fischer and Tillmanns (1988)
x y z Beq
Cal 4c m 0.0502(3) 0.25 0.1911(2) 1.90
Ca2 8d 1 0.1423(2) -0.0966(1) 0.1588(1) 1.95
Ca3 8d 1 0.3622(2) 0.0861(1) 0.0657(1) 1.85
Si 8d 1 0.3457(3) 0.0747(1) 0.3659(2) 1.68
S 4c m 0.0171(5) 0.25 0.5885(2) 2.17
01 4c m 0.233(1) 0.25 0.6028(8) 3.21
02 4c m -0.043(1) 0.25 0.4519(6) 2.23
03 8d 1 -0.062(1) 0.1717(3) 0.6504(5) 3.19
04 8d 1 0.3861(7) -0.0095(3) 0.2699(4) 1.93
05 8d 1 0.1805(7) 0.0511(3) 0.4751(4) 1.77
06 8d 1 0.2883(7) 0.1542(3) 0.2678(4) 1.92
07 8d 1 0.5319(7) 0.1092(4) 0.4537(5) 2.13

0 3
map revealed no electron density larger than 1 e/A-, confirming the ordered
distribution of S and Si. The refined atomic coordinates and equivalent isotropic
displacement factors are given in Table 3, a list of anisotropic displacement factors
is available from the authors on request.

Crystal structure
The crystal structure of ternesite is identical with the structure of synthetic
Ca5(SiO4)2SO4 determined by Brotherton et al. (1974). It consists of isolated SiO4
and SO4 tetrahedra connected via Ca ions which are coordinated by six or seven
oxygen atoms, respectively.
Some interatomic distance and angles of the tetrahedra are listed in Table 4. The
tetrahedra T(1)O4 lying on the mirror plane have an average interatomic distance
between the central atoms and the oxygen atoms of 1.467 A, which corresponds
to the average S - O distance of 1.473 A given by Baur (1981). In the tetrahedra
T(2)O4 in general position the average distance between the central atom and the
oxygen atoms is 1.638 A, which fits well to an expected Si-O distance for isolated
o

SiO4 tetrahedra of 1.637 A, calculated after Baur (1978).

There are three differently coordinated calcium ions, Ca1 is situated on a mirror
plane, while Ca2 and Ca3 occupy a general Wyckoff position, respectively. Some
interatomic distances of the Ca polyhedra are listed in Table 4. The Ca1 ions are
coordinated by seven oxygen atoms, which form an irregular one-capped trigonal
prism. A further oxygen atom (02 I) is rather near (Cal-O2' = 3.149(7) A), but its
distance is 27 percent larger as the average distance of the other ones, so it is not
considered to be part of the coordination polyhedron. Ca2 is coordinated by six
oxygen atoms, but there is also a further oxygen 0 3 I, that does not belong to the
coordination of Ca2 (Ca2-O3 ~ : 3.106(7) A). The six ligands form a polyhedron
 A new mineral from the Ettringer Bellerberg/Eifel 127
o

Table 4. Some interatomic distances [A], bond angles [ o], intrapolyhedral 0 - 0

distances (given in brackets) and bond valences s (after Brown and Altermatt,
1985)
[] [A] s [o] [A] s
S-O2 1.451(7) 1.60 Si-O6 1.628(5) 0.99
S-O3 2x 1.464(5) 1.54 Si-O5 1.629(5) 0.99
S-O1 1.489(8) 1.45 Si-O4 1.646(5) 0.94
<S-O> <1.467> Z=6.13 Si-O7 1.647(5) 0.94
<Si-O> <1.638> 2=3.86
O1-S-O2 112.1(5) [2.439(10)] O4-Si-O5 110.,3(2) [2.688(6)]
O1-S-O3 2x 109.1(3) [2.405(9)] O4-Si-O6 105.5(2) [2.607(7)]
O2-S-O3 2x 107.9(3) [2.356(7)] O4-Si-O7 116.4(3) [2.800(7)]
O3-S-OY 110.8(4) [2.410(7)] O5-Si-O6 114.7(3) [2.742(6)]
<O-S-O> <109.5> <2.395> O5-Si-O7 104.0(3) [2.581(7)]
O6-Si-O7 106.2(3) [2.619(7)]
<O-Si-O> <109.5> <2.673>

Cal-O6 2x 2.335(5) 0.37 Ca2-O1 2.575(3) 0.19

Cal-O6" 2x 2.362(5) 0.34 <Ca2-O> <2.401> Y~=l.91
Cal-O7 2x 2.624(6) 0.17
Ca 1-02 2.731 (7) 0.13 Ca3-O5 2.288(5) 0.42
<Cal-O> <2.482> Y,=1.89 Ca3-O7 2.303(5) 0.40
Ca3-O5' 2.322(5) 0.38
Ca2-O3 2.327(5) 0.38 Ca3-O6 2.364(4) 0.34
Ca2-O4 2.327(5) 0.38 Ca3-O4 2.552(4) 0.21
Ca2-O5 2.338(5) 0.37 Ca3-O2 2.611(2) 0.18
Ca2-O7 2.414(5) 0.30 Ca3-O3 2.617(5) 0.17
Ca2-O4' 2.424(5) 0.29 <Ca3-O> <2.437> Y,=2.10

O1 Y~=1.83 02 2=2.09
03 2=2.09 04 Y~=1.82
05 Y~=2.16 06 Y~=2.04
07 Y~=l.81

which can be called a transition between an octahedron and a trigonal prism. The
Ca3 ions are unambiguously surrounded by seven oxygen atoms, which form a
distorted pentagonal bipyramid.
The oxygen atoms O1, 0 2 and 0 3 form the apices of the SO4 tetrahedra and
they are coordinated by Ca and S in different ways: O1 and its three ligands (S and
two Ca atoms) form a flat trigonal pyramid, 0 3 also has three ligands, but is
trigonal planarly coordinated, the sum of the ligand-O3-1igand angles being
128 E. Irran et al.

Fig. 1. Crystal structure of ternesite projected along [100] (program ATOMS, Dowty, 1995)

360.0 . 02 is surrounded by S and three Ca atoms which form a heavily

compressed tetrahedron. In contrast, all oxygen atoms which are bound to silicon
(04 to 07) are coordinated by only slightly distorted tetrahedra of Si and three Ca
atoms, with average ligand-oxygen-ligand angles from 108.6 to 109.3 . The bond
valence sum of all seven oxygen atoms are given in Table 4.

Discussion
Gutt and Smith (1968) already recognised the similarity of the diffraction pattern
of synthetic Ca5(8iO4)2SO4 to the pattern of Cas(PO4)2SiO 4 ('silicocarnotite'),
which was confirmed by the crystal structure determination of both compounds
(Brotherton et al., 1974; Dickens and Brown, 1971). In addition there is a number
of synthetic compounds isotypic to ternesite which are listed in Table 5, some
interatomic distances of these compounds are given in Table 6.

The tetrahedra
In ternesite the distribution of the small atoms over the tetrahedra is as expected
by the formula, the sulfur atoms occupy the tetrahedra T(1)O4 in special position
and the silicon atoms the tetrahedra T(2)O4 in general position. In contrast, in
'silicocarnotite', Cd5(PO4)2SiO4 and Cds(PO4)2GeO4 the T(1)O4 tetrahedra are
filled by P only, but the other half of the P together with Si and Ge, respectively,
 A new mineral from the Ettringer Bellerberg/Eifel 129

Table 5. Isotypic compounds, their lattice constants and volume

a [/k] b [A] c [A] Vol. [A3] Lit.
Cas(SiO4)zSO4 6.863(1) 15.387(2) 10.181(1) 1075.1 1)
Cas(PO4)2SiO4 6.737(1) 15.508(2) 10.132(1) 1058.57 2)
Cas(CrO4)3 6.733(2) 16.097(3) 10.334(2) 1120.01 3)
Cas(CrO4)l.8(SiO4)l.2 6.725(4) 15.812(4) 10.249(10) 1089.83 3)
CdzsCazs(PO4)2SiO4* 6.655 15.328 10.104 1030.69 4)
Cds(PO4)2SiO4 6.692(2) 14.99(1) 10.140(5) 1017.17 4)
Cds(PO4)2GeO4 6.734(1) 15.107(2) 10.210(2) 1038.67 4)
Cds(AsO4)2SiO4* 6.751 15.328 10.326 1068.53 4)
Cds(AsO4)2GeO4* 6.800 15.427 10.416 1092.68 4)
Nafd4(PO4)3 6.670(2) 15.10(3) 10.04(2) 1011.20 5)
NaCd4(AsO4)3* 6.759 15.619 10.382 1096.02 4)
NaCd9(PO4)sSiO4* 6.654 15.064 10.121 1014.49 4)
* Only powder data available, standard deviation below 0.002 ,~. Literature: 1)
this work; 2) Dickens and Brown (1971); 3) Adendorffet al. (1992); 4) Engel and
Fischer (1985); 5) Ben Amara et al. (1979)

share the T(2)O4 tetrahedra (Dickens and Brown, 1971; Engel and Fischer, 1985).
As could be shown for Cd5(PO4)2SiO4 and Cds(PO4)2GeO4 this ordering is perfect,
while the average distances of the tetrahedra of 'silicocarnotite' may show a slight
disorder. Adendorff et al. (1992) suppose that in Cas(CrO4)3 the tetrahedra T(1)O4
are filled by formally tetravalent chromium and the tetrahedra T(2)O4 by formally
hexavalent chromium as indicated by the average central atom - oxygen distance,
but the distribution of the atoms shows a certain degree of disorder, too. The
distribution of the tetrahedrally coordinated atoms in Ca5(CrO4)l.8(SiO4)1.2 is more
complicated, the occupation factors of Cr and Si on the different tetrahedral sites
could be determined, but not the distribution of the different oxidation states of
chromium (Adendorffet al., 1992). In any way, the similar average distances show
a high degree of disorder. At least in NaCd4(PO4)3 the tetrahedra are occupied by P
only, although the T(1)O4 tetrahedra are slightly smaller than the T(2)O4 (Ben
Amara et al., 1979).
This review shows that the distribution of the small atoms over the tetrahedra is
mainly controlled by their size. The smaller P, Cr, and S atoms prefer the tetrahedra
T(1)O4, while the larger ones (Si, Ge, Cr) rather fill the T(2)O4 tetrahedra. This
results in an atomic distribution also found in normal, inverse, or partially inverse
spinels, though in the 'silicocarnotite'-group it is just a distribution between dif-
ferent kinds of tetrahedra and not between octahedral and tetrahedral voids as in
spinel.

The large cations

In the different compounds of the 'silicocarnotite'-group not only the size of the
coordination polyhedron of the large cations is varied, but also the number of
130 E. Irran et al.

Table 6. Comparison of interatomic distances of compounds isotypic to ternesite [A];

numbers in square brackets are not used for calculation of the average cation-anion
bond lengths
Cas(SiO4)~ Cas(PO4)2 Ca~(CrO4)3 Ca~(CrO4b Cds(PO4)2 Cds(PO4)2 NaCd4
SO4 SiO4 (SIO4)1.2 SiO4 GeO4 (PO4)3

T1-O2 1.451(7) 1.569(3) 1.673(5) 1.684(5) 1,545(6) 1.529(8) 1.527(3)

T1-O3 2x 1.464(5) 1.546(2) 1.705(3) 1.668(3) 1.527(5) 1.521(7) 1.524(2)
T1-O1 1.489(8) 1.5574(_43 1._.fi82(4) 1.676(6) 1.531(8) 1.551(12~ 1.553(4)
<Yl-O> <1.467> <1.555> <1.691> <1.674> <1.533> <1.531> <1.532>

T2-O6 1.628(5) 1.600(3) 1.735(2) 1.660(3) 1.578(4) 1,651(6) 1.535(6)

T2-O5 1.629(5) 1.596(2) 1.770(2) 1.659(3) 1.597(4) 1.628(6) 1.570(2)
T2-O4 1.646(5) 1.585(2) 1.721(2) 1.651(3) 1.577(4) 1.633(6) 1.540(2)
T2-O7 1.647(5) 1,608(2.23 1_~.736(3) 1.655(3) ~ 1.6587(7) 1.555(2.)
<T2-O> <1.638> <1.597> <1.741> <1.656> <1.586> <1.643> <1.550>

M1-O6 2x 2.335(5) 2.416(3) 2.459(2) 2.422(3) 2.271(4) 2.261(6) 2.329(3)

M1-O6" 2x 2.362(5) 1.417(3) 2.462(2) 2.434(4) 2.334(4) 2.334(6) 2.413(3)
M1-O7 2x 2.624(6) 2.570(3) 3.552(3) 2.564(3) 2.708(5) 2.746(8) 2.809(3)
M1-O2 2.731(7) 2.654(3) 2.741(5) 2.681(5) 2.380(6) 2.370(8) 2.381(3)
M1-O2' [3.149(7)_] 2.907(3) 2.811(5) 2.81k(_6.) [3.095(6)] [3.1790) ] 3.030(3)
<M1-O> <2.482> <2.546> <2.562> <2.534> <2.429> <2.436> <2.564>

M2-O3 2.327(5) 2.284(2) 2.298(2) 2.283(3) 2.193(4) 2.197(6) 2.185(2)

M2-O4 2.327(5) 2.443(2) 2.425(2) 2.396(3) 2.291(4) 2.290(6) 2.321(2)
M2-O5 2.338(5) 2.375(2) 2.384(2) 2.342(3) 2.395(4) 2.407(6) 2.410(2)
M2-O7 2.414(5) 2.517(2) 2.557(2) 2.514(3) 2.460(5) 2.464(7) 2.425(2)
M2-O4 2.424(5) 2.518(2) 2.529(2) 2.486(3) 2.496(4) 2.492(6) 2.463(2)
M2-O1 2.575(3) 2.423(2) 2.479(2) 2.508(2) 2.307(3) 2.288(5) 2.307(2)
M2-O3' [3.105(7).] 2.694(3) 2.600(3) 2.704_C4~ I2.967(6)_1 [2.952(9).] [2.878(3)_1
<M2-O> <2.401> <2.465> <2.467> <2.462> <2.357> <2.365> <2.352>

M3-O5 2.288(5) 2.317(2) 2.238(2) 2.306(3) 2.259(4) 2.261(6) 2.278(2)

M3-O7 2.303(5) 2.299(2) 2.325(3) 2,306(3) 2.208(4) 2.216(7) 2.230(2)
M3-O5' 2.322(5) 2.324(3) 2.367(2) 2.328(3) 2.284(4) 2.310(5) 2.315(3)
M3-O6 2.364(4) 2.408(2) 2.442(2) 2.433(3) 2.366(4) 2.339(7) 2.290(2)
M3-O4 2.552(4) 2.624(2) 2.651(2) 2.599(3) 2.768(4) 2.809(6) 2.791(2)
M3-O2 2.611(2) 2.485(2) 2.562(1) 2.540(1) 2.491(2) 2.522(3) 2.421(2)
M3-O3 2.617(5) 2,493(2) 2.494(2) 2.517(3_) 2.350(4) ~ 2,386(2)
<M3-O> <2.437> <2.421> <2.440> <2.433> <2.389> <2.400> <2.387>

ligands can be changed. At the M1 position (conferring to the C a l position in

ternesite) in 'silicocamotite', Ca5(CrO4)3, and Ca5(CrO4)l.8(SiO4)l.2 the calcium
ions are coordinated by eight o x y g e n atoms, in contrast to the seven-coordinated
C a l in temesite. In Cds(PO4)2SiO4, and Cds(PO4)zGeO4 the smaller Cd ions have
seven ligands, the larger Na ion in NaCd4(PO4)3 again is coordinated by 8 oxygen
atoms. In all cases o f 8-coordination, the eighth ligand is an 0 2 atom. A similar
situation is found for the M2 position, in Cas(PO4)2SiO 4, Cas(CrO4)3, and
Cas(CrO4)l.s(SiO4)l.2 the Ca2 ions have one m o r e ligand than the Cd2 and the
 A new mineral from the Ettringer Bellerberg/Eifel 131

Ca2 ions in Cds(PO4)2SiO4, Cds(PO4)2GeO4, and ternesite, respectively, resulting

in a seven-coordination instead of a six-coordination in the latter compounds. The
additional ligand in all cases is an 0 3 atom. In contrast, the M3 position is co-
ordinated in the same way for all compounds of the group.

The oxygen atoms

As a consequence of the higher coordination of the Ca ions in Cas(PO4)2SiO4,
Cas(CrO4)3, and Cas(CrO4)1.8(SiO4)l.2 the oxygen atoms 0 2 and 03 have one
ligand more than in the other compounds, resulting in a 5- and 4-coordination,
respectively. As both 0 2 and 0 3 are ligands of the T(1)O4 tetrahedra only, the
average coordination number of the oxygen atoms of both the T(1)O4 and T(2)O4
tetrahedra is four. The bond lengths between the central atom and the ligands in a
coordination polyhedron depends strongly on the coordination number of the lig-
ands, so the size of the T(1)O4 and T(2)O4 tetrahedra should be more similar in the
Ca-containing Cas(PO4)2SiO4, Cas(CrO4)3, and Ca5(CrO4)l.8(SiO4)l. 2. This may
be the reason for the higher disorder of the tetrahedrally coordinated atoms. The
reason, why ternesite shows a fully ordered occupation of the tetrahedra though it
also contains Ca may be the large difference between the effective ionic radii of Si
(0.27 A) and S (0.12 A) (ionic radii after Shannon, 1976).

Acknowledgements
Samples of ternesite were kindly provided by Mr. B. Ternes, Mayen, Germany. Thanks are
due to Dr. G. Giester, Dr. Ch. Lengauer, Dr. E. Libowitzky, and Mr. P. Nagl for fruitful
discussions and help with experimental procedures. Financial support by JCPDS/ICDD,
Newtown Square, PA, USA under grant 90-03 to ET is gratefully acknowledged.

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Authors' addresses: E. Irran, Laboratorium ftir Anorganische Chemie I, Universit~it

Bayreuth, Universit~itsstrasse 30, D-95440 Bayreuth, Federal Republic of Germany; E.
TiIlmanns, Institut ftir Mineralogie und Kristallographie der Universit/it, Geozentrum,
Althanstrasse 14, A-1090 Wien, Austria; G. Hentschel, Schillerstrasse 1, D-53489 Sinzig 2,
Federal Republic of Germany.
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