Lithos 134-135 (2012) 75–90

Contents lists available at SciVerse ScienceDirect

Lithos
journal homepage: www.elsevier.com/locate/lithos

Natural pseudowollastonite: Crystal structure, associated minerals, and

geological context
Yurii V. Seryotkin a, b,⁎, Ella V. Sokol a, Svetlana N. Kokh a
a
Sobolev Institute of Geology and Mineralogy, Siberian Branch of Russian Academy of Sciences, 3 Koptug Avenue, Novosibirsk, 630090, Russia
b
Novosibirsk State University, 2 Pirogova str., Novosibirsk, 630090, Russia

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

Article history: Pseudowollastonite, an extremely rare constituent of ultrahigh-temperature combustion metamorphic and
Received 29 September 2011 igneous rocks, has been found as a rock-forming mineral in Ca-rich paralava veins of Nabi Musa fossil mud
Accepted 17 December 2011 volcano (Dead Sea area). Pseudowollastonite-bearing paralavas are the products of combustion metamor-
Available online 27 December 2011
phism associated with spontaneous burning of methane. The melt began to crystallize at 1480–1500 °C
about the ambient pressure. Pseudowollastonite enters two mineral assemblages: (1) rankinite, larnite,
Keywords:
Pseudowollastonite
nagelschmidtite, wollastonite (1T), gehlenite-rich melilite, Ti-rich andradite, cuspidine, and fluorapatite;
Parawollastonite (2) parawollastonite (2M), wollastonite (1T), gehlenite-rich melilite, Ti-rich andradite, fluorellestadite. In
Wollastonite this study we present the first single-crystal structure determination of natural pseudowollastonite. Pseudo-
Combustion metamorphism wollastonite from Nabi Musa dome is stoichiometric CaSiO3 and belongs to the most widespread four-layer
Mottled Zone polytype: a = 6.83556(10) Å, b = 11.86962(18) Å, c = 19.6255(3) Å, β = 90.6805(13)°, V = 1592.21(4) Å 3,
space group C2/c. We argue that pseudowollastonite is so scarce in nature because its formation requires
joint action of several uncommon factors: availability of hot melts of T > 1200 °C that bear free calcium but
are poor in Mg and Fe (mostly as Fe 3 +) and their crystallization in the shallow crust followed by quenching.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction and settings of natural pseudowollastonite-bearing paralava found at

Pseudowollastonite is an extremely rare mineral in natural environ-
ments, unlike widespread wollastonite-1T and 2M (parawollastonite).
Until recently it has only been reported from three localities of specific
ultrahigh-temperature and very low pressure Ca-rich combustion
metamorphic (CM) rocks (paralavas and hornfels) produced by sponta-
neous ignition of high-calorific hydrocarbons. One locality lies within
the rich Chillingar oil-field in Iran (McLintock, 1932) and two others
occur in the so-called Mottled Zone (MZ) complexes in Israel (Gross,
1977; Sokol et al., 2008, 2010). Recently Stoppa and Sharygin (2009)
have mentioned pseudowollastonite as a sporadic phase in mantle-
derived melilitolite of Colle Fabbry, Italy. Although being approved by
CNMNC (http://pubsites.uws.edu.au/ima-cnmnc/imalist.htm), pseudo-
wollastonite has been paradoxically represented in the Mineral Data-
base by its synthetic counterpart (CaSiO3, space group C2/c) (Yang
and Prewitt, 1999a) for the lack of data on the natural mineral species.
In this paper we use a variety of analytical tools, such as petrography,
electron microprobe, both single-crystal and powder X-ray diffraction, as
well as X-ray fluorescence, to characterize the mineralogy, chemistry,
⁎ Corresponding author at: Sobolev Institute of Geology and Mineralogy, Siberian
Branch of Russian Academy of Sciences, 3 Koptug Avenue, Novosibirsk, 630090, Russia.
Tel.: + 7 383 333 24 06; fax: + 7 383 333 27 92.
E-mail addresses: yuvs@igm.nsc.ru (Y.V. Seryotkin), sokol@igm.nsc.ru (E.V. Sokol),
s.n.kokh@gmail.com (S.N. Kokh).
Nabi Musa fossil mud volcano in the Dead Sea area. These peculiar
ultrahigh-temperature melt rocks result from combustion metamor-
phism caused by spontaneous natural burning of methane in the
Middle–Late Pleistocene. Our primary objectives were to determine
the structure of natural pseudowollastonite, which has never been
done before, and to investigate the geological context of its appearance.
2. Polymorphism and polytypism in wollastonite and
pseudowollastonite under ambient pressure
Calcium metasilicates (CaSiO3) are represented by a significant
number of polymorphs and polytypes (Mazzucato and Gualtieri,
2000). The low-pressure CaSiO3 polymorphs are wollastonite and
pseudowollastonite. The most common CaSiO3 polymorph is single-
chain silicate wollastonite-1T (space group P1) (Fig. 1a), which is a
rock-forming mineral in the Earth's upper crust (Deer et al., 1997).
Pseudowollastonite has a structure with isolated trisilicate rings
[Si3O9] (Fig. 2); it is stable above 1125 °C ± 10 °C and melts congru-
ently at 1548 °C ± 10 °C. The wollastonite-1T–pseudowollastonite
phase boundary has a positive slope and terminates at the solidus at
about 2.3 GPa and 1607 °C (Essene, 1974; Richet et al., 1998; Swamy
and Dubrovinsky, 1997). As a consequence, pseudowollastonite being
a common constituent of slag and ceramic substances is restricted in
its natural occurrences by very uncommon ultrahigh-temperature–

0024-4937/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.lithos.2011.12.010
76 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90

Fig. 1. Crystal structures of wollastonite (a) and parawollastonite (b) along the c-axis. The stacking sequences of (100) slabs for wollastonite polytypes (c) according to Henmi et al.
(1983). Thick lines indicate the unit cells.

low-pressure geological environments (Gross, 1977; McLintock, 1932;
Sokol et al., 2008, 2010).
The structure of wollastonite and its polytypes is formed with the
(SiO3) ∞ chains directed along the b axis. The Ca atom coordination is
distorted octahedron with Ca\O bond lengths of 2.22–2.65 Å. The
chains are shifted relative to each other, changing the periodical
basis along the a axis. Crystal structures of wollastonite polytypes
may be described in terms of stacking of (100) slabs, each of about
7.7 Å thickness (a parameter of wollastonite structure, Fig. 1a).
Thus, parawollastonite structure may be described by the combina-
tion of two wollastonite slabs, one located in a continuous position
with respect to the preceding one (T in notation of Henmi et al.,
1983) and the second slab (G) is displaced by b/2 (Fig. 1b).
Wollastonite-1T is a one-layer polytype, while the two-layer se-
quence generates monoclinic polytype wollastonite-2M (parawollas-
tonite, space group P21/a, Trojer, 1968). Multilayer blocks contain
alternative slabs T and G, forming various wollastonite polytypes,
including 3T, 4T, 5T, and 7T ones (Fig. 1c), which were discovered
by Henmi et al. (1978, 1983).
The same mechanism explains existence of the epitaxial inter-
growth of wollastonite polytypes within one crystal, where they
form individual lamellae. Indeed, the possibility of slab joining along
joint (100) plain at the structure level (Fig. 1b,c) permits to join the
macrocrystals of two and more wollastonite polytypes also. This
type of phase relations between wollastonite-1T and 2M was supported
by optical observations (Deer et al., 1997) and by TEM experiments
(Hutchison and McLaren, 1976).
The twinning plane of CaSiO3 polytypes is not parallel to oxygen
closest-packed layers. Thus the wollastonite polytypes cannot be
regarded as unique stacking of tetrahedral and octahedral layers,
which is the case for structurally similar enstatite. Therefore, ortho-
and clinoenstatite transform rapidly as temperature changes, where-
as no direct transformation between wollastonite-1T and 2M has
been ever observed (Ohashi, 1984). Mazzucato and Gualtieri (2000)

Fig. 2. Comparison of stacking sequence of layers of [Si3O9] rings in (a) two- and (b) four-layer pseudowollastonite polytypes.
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90
have reported that in the temperature range 700–1000 °C
wollastonite-1T forms as the earliest phase and progressively trans-
forms in an intermediate wollastonite-1Td, a completely disordered
triclinic form. They assume that both phases, in turn, transform into
the wollastonite-2M polytype.
In addition to the polymorphic modifications discussed so far, poly-
types based on the wollastonite-1T and pseudowollastonite structures
have been identified as well (Ingrin, 1993; Mazzucato and Gualtieri,
2000). Wollastonite and pseudowollastonite crystal structures are
different radically. Pseudowollastonite structure characterized by
layers, each of which is composed of a layer of ternary [Si3O9] rings
and a layer of distorted-bicapped Ca octahedral (Fig. 2).
So far pseudowollastonite polytypism has been studied using syn-
thetic crystals only. Yamanaka and Mori (1981) were the first who
identified four-layer, six-layer, and disordered stacking polytypes of
pseudowollastonite crystals, and determined the crystal structure of
a 4-layer polytype in the space group C1. Ingrin (1993) recognized
three polytypes of 2-, 4- (dominant phase), and 6-layers coexisting
in one sample as (001) lamellae ranging in width from one to several
unit cells. The polytype lamellae remained stable after prolonged
annealing at temperatures greater than 1700 K. Thus, the 4-layer
polytype was suggested not to be the most stable phase over the
whole temperature range of pseudowollastonite stability. Yang and
Prewitt (1999a) re-determined the structure of high-quality synthetic
pseudowollastonite crystals and showed that the four-layer polytype
had monoclinic C2/c rather than triclinic C1 symmetry. Shortly after
the same authors (Yang and Prewitt, 1999b) determined the structure
of a two-layer pseudowollastonite polytype, space group C2/c.
Polytypism of pseudowollastonite is based on the variation of the
stacking sequences of the displaced layers of ternary rings with
undisplaced layers. In the two-layer structure, the second layer is dis-
placed one-sixth of the a dimension with respect to the first layer
(Fig. 2a). In the four-layer structure, the first and second layers of ter-
nary rings are stacked directly on top of one another, whereas the
third layer is displaced one-sixth of the b axis with respect to the second
layer (Fig. 2b). The fourth layer lies directly on top of the third layer.
Note that the a and b axes in the two-layer structure are reversed
with respect to those in the four-layer structure (Yang and Prewitt,
1999b). This method permits to describe the polytype structure with
an arbitrarily large sequence of layers.
3. Pseudowollastonite occurrences in natural environments
3.1. Darreh Harrachi, Iran
McLintock (1932) was the first who discovered pseudowollastonite
in nature. The mineral was identified in annealed and fused marl asso-
ciated with the combustion of hydrocarbons (gas and oil) from Darreh
Harrachi locality in SE Iran at the head of the Persian Gulf. The area
lies on the extension of a long anticline fold (the Chillingar axis)
where a prolific oil reservoir was found in 1974. A compact body
(2.5 × 3.5 m) of greenish vesicular crystalline combustion metamorphic
melt rocks surrounded by colored slightly brecciated marls was found
above a vertical cliff of Middle Fars (Miocene) limestone. The thermally
altered rock was formed after the marls and resembled a dike or a plug,
but no chilled margins were observed. CM rocks were continuous
downwards, with baked mudstone underlain by bituminous limestone,
with well-developed vertical joints carrying bitumen. Field evidence in-
dicated a vent structure resulting from explosive escape of oil and gas
that became ignited causing thermal alteration and fusion of sedimen-
tary rocks.
Melted and porcellanous-type CaSiO3-bearing CM rocks from Darreh
Harrachi and Tul-i-Marmar districts have major-oxide compositions
with 24.19 to 31.77 wt.% CaO, 5.77–8.67 wt.% MgO, and 0.56–1.28 wt.%
FeO (Table 1). Their dry liquidus temperatures were estimated by
Grapes (2011) by means of MELT program to be as high as
77
1190–1330 °C. Unfortunately, McLintock (1932) inferred the chemical
and mineralogical compositions of the samples that contained pseudo-
wollastonite from optical properties only without analyzing them. The
refractive indexes of wollastonite (α=1.617, β =1.628, γ =1.630) and
pseudowollastonite (ω =1.614, ε= 1.6148) he reported are very close
to those of pure wollastonite and pseudowollastonite, correspondingly
(Deer et al., 1997).
Most of paralava samples described in McLintock (1932) bear wollas-
tonite. Pseudowollastonite as a rock-forming mineral was discovered in
three out of eight samples. It was detected in intimate association with
colorless melilite (gehlenite–akermanite solid solution ?) +yellow py-
roxene (aegirine–augite ?) +turbid wollastonite, and deep-brown
glass. Pseudowollastonite built irregularly-shaped crystal grains
(0.05–0.1 mm) or irregular prisms, with corroded outlines. Besides indi-
vidual grains, two CaSiO3 polymorphic modifications coexisted within
the same crystals which may consist of a pseudowollastonite core
rimmed by wollastonite. McLintock (1932) interpreted those inter-
growths as evidence for “partial reversion” of pseudowollastonite to
wollastonite.
3.2. Hatrurim Basin, Israel
Other CM rocks containing pseudowollastonite were reported
from in the Mottled Zone of the Hatrurim Basin area near the Dead
Sea (Gross, 1977). The mineral was identified in three samples
only, but it formed up to 15 vol.% of the rock composed of rankinite,
gehlenite, schorlomite, and larnite. It was found mostly as elongat-
ed, poikiloblastic (filled with minute gehlenite crystals), colorless
crystals up to 0.5 mm across, the larger crystals being frequently
twinned, with no more than four individuals. In one sample drop-
like pseudowollastonite grains (20 μm) were hosted by rankinite.
Gross (1977) made the first microprobe analyses of pseudowollas-
tonite and detected a major-oxide composition with 48.20 CaO,
51.92 SiO2 (in wt.%), and traces of MgO. Thirty years later pseudo-
wollastonite was found in the same place (the Gurim anticline) in
hornfelses composed of gehlenite–akermanite melilite, wollaston-
ite, Ti-rich andradite, fluorapatite, and Cr-rich spinel (Sokol et al.,
2008); pseudowollastonite laths tended to be mainly concentrated
around vesicles.
3.3. Colle Fabbri, Central Italy
Colle Fabbri is one more locality where pseudowollastonite was
identified from a subvolcanic body of larnite-normative melilitolite
intruding sedimentary rocks and overlain by an extrusive breccia.
The Colle Fabbri melilitolite consists of gehlenite–akermanite, wollaston-
ite, leucite (or kalsilite), and accessory Ti-garnet, Ti–Al–Fe3 +-clinopyrox-
ene, magnetite, perovskite, rankinite, Si-bearing apatite, Fe–Ni sulphides,
and carbonate/zeolite. The majority of contact rocks contaminated by
pelitic material contain clinopyroxene, anorthite, wollastonite, sanidine,
spinel and glass. XRD indicated most of wollastonite to exist as the 1T
CaSiO3 modification but revealed pseudowollastonite in a few melilito-
lite samples. Wollastonites from the Colle Fabbri igneous rocks mainly
bear some FeO (commonly 2.07–2.25 wt.%, rarely up to 12.50 wt.%)
and MgO (0.19–1.99 wt.%), at quite low MnO (to 0.47 wt.%) and likely re-
semble Ca-bustamite (Table 2) (Melluso et al., 2003; Sharygin, personal
communication; Stoppa and Sharygin, 2009). As for pseudowollastonite,
it has not been characterized in Stoppa and Sharygin (2009) and is
known only from unpublished evidence by Prof. F. Scordari (University
of Bari, Italy) that two examined pseudowollastonite crystals were
four-layer polytypes close to pure CaSiO3. Crystallization of melilitolite
began at T >1308 °C while the contact igneous rocks crystallized at
T> 1230 °C. Wollastonite-hosted inclusions were homogenized under
T= 1195–1240 °C (Stoppa and Sharygin, 2009).
78 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90

Table 1
Compositions of CaSiO3-bearing combustion metamorphic hornfels, paralava and melilitite (wt.%).

Locality Hatrurim Basin Colle Fabbri Tul-i-Marmar Darreh Nabi Musa

Harrachi

Rock sample h-07- G-4-3v h-40 SVK17 SVK11 SVK10 CF5 CF1 F.3027 F.3030 F.3029 F.3084 21 12D 12C YV-
51-3 197

SiO2 33.95 36.09 32.17 45.50 48.30 52.90 40.30 52.90 44.73 45.11 43.29 42.35 46.53 36.00 35.00 38.50
TiO2 1.41 2.03 0.58 0.48 0.50 0.65 0.45 0.63 0.85 0.83 0.73 0.68 0.21 0.42 0.21 –
Al2O3 8.26 7.28 15.44 9.0 12.3 13.2 10.40 13.8 10.30 9.63 9.27 8.71 1.93 6.00 2.01 4.40
Fe2O3 7.61a 8.54a 8.51a 4.08a 5.13a 5.61a 1.40 3.63 3.89 3.64 4.01 2.78 1.81a 2.80a 1.30a 1.90a
FeO 2.03 1.92 1.28 1.22 0.56 0.72
MnO 0.12 0.11 0.14 0.08 0.04 0.10 0.07 0.11 0.12 0.01 0.06
MgO 0.60 0.54 0.63 1.72 2.86 1.99 1.80 3.46 5.77 5.87 8.40 8.67 0.32 1.00 0.50 0.80
CaO 41.41 40.57 35.53 36.8 26.6 21.2 38.70 18.2 24.19 25.17 28.83 31.77 44.38 48.10 50.10 51.00
Na2O 0.35 0.34 0.43 0.49 1.09 0.68 0.47 0.72 1.60 2.26 1.37 1.53 0.28 0.40 0.40 0.30
K2O 0.41 1.25 0.37 1.59 1.80 2.31 1.38 1.83 2.72 0.83 2.16 1.51 0.10 0.20 0.20 0.20
P2O5 1.78 1.87 2.13 0.10 0.05 0.15 0.11 0.12 0.15 0.14 0.15 0.07 0.89 1.10 0.80 0.70
F 0.48 0.23 0.11 0.15
LOI 4.50 2.22 4.64 0.48 2.38 1.48 0.13 2.69 4.89 5.67 1.27 1.07 3.86 3.00 9.20 2.20
Total 100.40 99.59 100.57 100.32 101.05 100.27 100.00 100.00 100.37 100.37 100.04 99.86 100.43 99.03 99.72 100.06
CaO/SiO2 1.22 1.12 1.10 0.81 0.55 0.40 0.96 0.34 0.54 0.56 0.67 0.75 0.95 1.34 1.43 1.32
T estimations, 1050–1190 1195–1240 1190–1330b 1280–1500
°C
CaSiO3 Prw, Wo Pwo, Wo Wo Wo Fe-Mg- Wo Wo Wo Wo Wo, Pwo Prw, Wo, Pwo, Pwo, Pwo,
modifications Wo Wo Wo Pwo Wo Wo Wo

Hatrurim Basin, Israel, data from Sokol et al. (2008) and unpublished data of the authors. Hornfels: h-40: Mel, Pwo, Wo, Ti-Adr, Ap-(F), Cr-Spl, CSHs.
Paralavas: G-4-3v: Wo, Mel, Rnk, Ti-Adr, Ap-(F), Kls, Nag, Mag, Hem; Prv, Tob 10 Å. h-07-51-3: Prw, Mel, Rnk, Ell-(F), Ti-Adr, Tob 10 Å.
Igneous rocks from Colle Fabbri, Italy (Melluso et al., 2003). SVK17: Wo, Mel, Pl, CPx, Lct, Grt, Prv, and opaque minerals. SVK11: Wo, Pl, CPx, and opaque minerals. SVK10: Pl, Wo, CPx,
and glass.
Igneous rocks from Colle Fabbri, Italy (Stoppa and Sharygin, 2010). CF5: Wo, Mel, Lct, Kls, Pl, Grt, CPx, Prv, Spl, Ap-(F). CF1: Pl, CPx, Wo, Gl, Mag, Spl, Ttn, Kfs, OM.
Paralavas after fused marls, Tul-i-Marmar and Darreh Harrachi, Iran (McLintock, 1932). F.3027: Wo, Aug, Pl, Gl, Cal, Gp. F.3029: Aug, Wo, Mel, Lct(?). F.3030: Aug, Wo, Mel, Gl, Cal.
F.3084: Di, Wo, Mel — (in the similar sample F.3083 Pwo + Wo + Mel + CPx were indentified).
Ap-(F) = fluorapatite, Aug = augite, Cal = calcite, CPx = clinopyroxene, Cr-Spl = Cr-spinel, CSHs = calcium silicate hydrates, Di = diopside, Ell-(F) = fluorellestadite, Gl = glass,
Gp = gypsum, Grt = garnet, Hem = hematite, Kfs = K-feldspar, Kls = kalsilite, Lct = leucite, Mag = magnetite, Mel = melilite, Nag = nagelshmidtite, OM = opaque mineral, Pl =
plagioclase, Prv = perovskite, Prw = parawollastonite, Pwo = pseudowollastonite, Rnk = rankinite, Spl = spinel, Ti-Adr = Ti-andradite, Ttn = titanite, Tob 10 Å = tobermorite
10 Å; Wo = wollastonite. Mineral symbols according to Whitney and Evans (2010).
a
All iron analyzed as Fe2O3.
b
Temperature estimations according to Grapes (2011).

4. Geological setting of Nabi Musa dome
There are fifteen complexes composed of peculiar rocks known as
the Mottled Zone, or the Hatrurim Formation, on both sides of the
Dead Sea Transform, in Israel and Jordan. Commonly the MZ com-
plexes rise above the surrounding Upper Cretaceous marine sedi-
ments as conical hills largely composed of diverse brecciated and
hydrothermally altered sedimentary and metasedimentary rocks. All
strata are densely veined and altered by late hydrothermal solutions.
Various Ca-rich combustion metamorphic rocks such as spurrite and
brownmillerite marbles, larnite rocks, melilite and anorthite–diop-
side hornfelses occur as spots in the mélange sequence (Burg et al.,
1999; Sokol et al., 2007, 2008, 2010; Techer et al., 2006; Vapnik et
al., 2007). Annealing of calcareous and marly sedimentary parent
rocks under high (750–1000 °C) or ultrahigh (1200–1500 °C) tem-
peratures and ambient pressure lead to the formation of peculiar as-
sociations of anhydrous Ca–Al–(Fe)-oxides and Ca silicates that are
typical of both sanidinite facies (Gross, 1977; Matthews and Gross,
1980; Sharygin et al., 2008; Sokol et al., 2010; Vapnik et al., 2007)
and pyrometamorphic rocks (Grapes, 2011; Reverdatto, 1973). For a
long time the appearance of CM foci was commonly attributed to in
situ subsurface spontaneous combustion of Senonian bituminous
chalks (Bentor et al., 1963; Burg et al., 1999; Gross, 1977). However,
the Mottled Zone structures differ significantly from CM complexes
produced by ignition of solid fuel, namely coal and oil shale (Sokol
et al., 2007; 2008; 2010; Vapnik et al., 2007). They resemble very
much CM complexes from Iran and Iraq, and to some extent those
in California, associated with expulsion of hydrocarbons from under-
lying gas accumulations and subsequent gas flaming (Basi and Jassim,
1974; Cisowski and Fuller, 1987; Lore et al., 2002; McLintock, 1932).
Recently a bulk of features characteristic of fossil mud volcanoes
was found at typical Mottled Zone localities that were studied in de-
tail, with reference to geological setting, geochemistry, and mineralogy
of coexisting sedimentary, hydrothermally altered, and ultrahigh-
temperature CM rocks. They are the Hatrurim Basin in Negev Desert
(Sharygin et al., 2008; Sokol et al., 2007, 2008; Vapnik et al., 2007)
and Nabi Musa dome in Judean Desert (Khesin et al., 2010; Sokol et
al., 2010).
Pseudowollastonite and parawollastonite occur as rock-forming
minerals in paralavas, unusual melt rocks found within Nabi Musa
dome which is located between Jerusalem and the northern end of
the Dead Sea (31°48′N, 35°25′E). The Nabi Musa hill is a topographic
expression of a slightly eroded fossil mud volcano edifice with two
conduits and craters. The main well-marked crater, widening upward
to about 80 m, lies under the western crest of the dome. It looks like a
huge funnel structure of brick-red, brown, and black rocks standing
out against chalky-like country rocks, and appears to be a pile of di-
verse breccias on closer examination. The clastics in the crater mainly
consist of Cretaceous sedimentary rocks derived from depths no more
than a few hundred meters. The rock infill of the eastern crater was
subjected to quite strong later hydrothermal alteration, mainly car-
bonation attendant with sulphatization and precipitation of Ca hydro-
silicates. Both funnels contain numerous in situ CM foci of mainly
spurrite, larnite, gehlenite, and brownmillerite rocks, with branching
paralava veins. The funnel shape of the main and satellite conduits, brec-
ciated sedimentary rock abundance and numerous high-temperature
CM centers suggest a diatreme origin of Nabi Musa dome formed by re-
peated explosive release and ignition of hydrocarbon gas. For details of
local geology and characteristics of rocks of the Nabi Musa complex see
Sokol et al. (2010).
Numerous branching paralava veins are mainly located in mélange
rocks within the central part of the funnel structures (Fig. 3a,b). The
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90 79

majority of paralavas are mainly subjected to deep hydrothermal alter-

1.000
0.000
0.000
1.000
0.00

0.04

0.00
100.20
51.69

48.47
ation and has been converted to specific “pebbles” encrusted with
Wo
19
calcium carbonate, silicate hydrate, and sulfate (Fig. 3c,d). Neverthe-
less, some paralava bodies preserve clear vein-like appearance and

0.996
0.034
0.029
0.934
0.19
0.09
2.07
0.10
0.98

0.02
50.30

44.00

97.76
form numerous thin branches off the main vein. All veins are rootless;
Wo
18

their total length is 0.5–1 m, rarely up to 4 m, and the width varies

from 1 to 10 cm. The orientation is governed by nearly horizontal

0.987
0.211
0.031
0.766
49.00

12.50

35.50

98.82
0.26
0.02

0.47
1.02

0.10
zones of brecciation and vertical fractures. Significant vein swelling
Bst
17

(up to 35 cm) is observed when a sub-vertical vein encounters a brecci-

15–18 = igneous rocks from Colle Fabbri, Italy: 15 = sample CF-21, data from (Stoppa and Sharygin, 2010); 16 = sample CF-1 V, unpublished data of V.V. Sharygin; 17, 18 = data from Melluso et al. (2003).
ation zone.

0.995
0.037
0.006
0.951
51.06

45.51

99.72
0.04
0.24
2.25
0.43
0.19

0.00
0.00
Wo
16

5. Analytical methods

0.991
0.170
0.059
0.777
0.20

0.43
1.99
50.02

10.29

36.60

99.53

The compositions of combustion metamorphic rocks from the Nabi

Bst
15

Musa and Hatrurim Basin localities (Table 1) were determined by

X-ray fluorescence (XRF) spectroscopy on a Karl Zeiss Jena (Jena)
0.998
0.000
0.003
0.999
51.53

48.11

99.81
0.03
0.00
0.00
0.00
0.09

0.05
0.00

VRA-20 R analyzer calibrated against the rock standards SG-1,2,3 (gran-

Prw
14

ite), SGD-1A (essexite gabbro), and MU-1 (peridotite). Detection limits

for most elements were 0.02 wt.% with 0.2 wt.% for Na2O and 0.1 wt.%
0.989
0.000
0.001
1.018
0.05
0.01
0.00
0.06
0.10

0.04
0.00
100.95
51.52

49.15

for MgO. Mineral and glass compositions of four pseudowollastonite-

Prw

bearing paralavas were determined from petrographic examination,

13

X-ray powder diffraction (XRPD), scanning electron microscopy

0.990
0.000
0.003
1.014

(SEM), and electron microprobe (EMPA) methods. XRPD analysis was

0.01
0.02
0.00
0.00
0.04

0.01
0.00
100.49
51.22

49.20
Prw

carried out using a DRON-3 X-ray powder diffractometer (CuKα-radia-

12

tion, graphite monochromator). SEM analyses were made using JSM

6380LA scanning electron microscope, and EPMA compositions were
0.992
0.001
0.000
1.008
0.05
0.01
0.06
0.01
0.06

0.00
0.00
100.21
51.29

48.62

obtained using Camebax-Micro and JXA-8100 electron microprobes

Wo
11

with an accelerating voltage of 20 kV, a count time of 10 s, a beam

current of 15–30 nA, and a beam diameter of 2–3 μm for anhydrous
0.995
0.001
0.002
1.003
0.03
0.03
0.03
0.00
0.09

0.05
0.00
100.44
51.26

48.96

minerals and glass. Estimated precision was better than 2% for all
Wo

major elements. The thermal behavior of powder samples was studied

10

by simultaneous TG-DTA thermal analysis (Q-150D apparatus). Sam-

Composition of CaSiO3 modifications from Nabi Musa paralava, Hatrurim Basin hornfels, and Colle Fabbri melilitite (wt.%).

0.995
0.000
0.000
1.009

ples in ~400–800 mg aliquots were run in Pt crucibles and heated at

0.00

0.00

0.00
51.23

48.46

99.69

10 °C/min from 25 to 1100 °C under flowing air with the weight and
Wo
9

heat flow monitored every 2 s.

The optically homogeneous crystals of pseudowollastonite (sam-
0.992
0.001
0.000
1.015
51.20

48.92
0.00

0.06

0.00
100.12

ple YV-197), wollastonite, rankinite, Ti-rich andradite (12D), and

Pwo

2–14 = paralavas from Nabi Musa, Israel: 2–5 = sample 12D; 6–9 = sample YV-197; 10–14 = sample 21.
8

parawollastonite (21) were selected for an X-ray single-crystal dif-

fraction study with the use of an Oxford Diffraction Xcalibur Gemini
0.994
0.000
0.000
1.012
51.40

48.84
0.00

0.00

0.00
100.24

diffractometer (MoKα-radiation, graphite monochromator). Diffrac-

Wo

tion data were collected with ω scans in full sphere of reciprocal

Bst = bustamite, Prw = parawollastonite, Pwo = pseudowollastonite, Wo = wollastonite.
7

space. Data reduction, including a background correction and Lorentz

0.999
0.000
0.000
1.002

and polarization corrections, was performed with the CrysAlis Pro

51.81

48.53
0.00
0.01
0.00
0.00
0.00

0.00
100.34
a
Pwo

software. A semi-empirical absorption correction was applied using

6

the multi-scan technique. The structures were determined with

SHELX-97 program package (Sheldrick, 2008). Experimental details
0.997
0.000
0.000
1.006

Pseudowollastonite crystal selected for single-crystal X-ray analysis.

51.77

48.72
0.00

0.01

0.00
100.50

1 = hornfels from Hatrurim Basin, Israel, data from Sokol et al. (2008).

for the data collection and structure determination of CaSiO3 poly-

Wo

morphs are given in Table 3.

5

19 = EMPA mineral standard of synthetic wollastonite (Wol-1).

0.994
0.000
0.000
1.012
51.38

48.86
0.00

0.02

0.00
100.26

6. Sample selection, paralava bulk chemistry and petrography

Pwo
4

Pseudowollastonite-bearing paralava veins occur under the eastern

0.997
0.000
0.000
0.999

crest of Nabi Musa dome (Fig. 3). Samples 12C, 12D, and YV-197 of the
0.04
0.06
0.02
0.00
0.00

0.06
0.04
100.44
51.76

48.42

freshest paralavas were selected from a compact paralava cluster located

Wo

Cations calculated on the basis of 3 oxygens

3

under the eroded dome surface at a depth of 7 m. The veins (up to

0.5–1 m long and 3–10 cm wide) are hosted by baked breccias partially
0.997
0.001
0.001
1.000
0.04
0.03
0.05
0.01
0.03

0.02
0.01
100.80
51.98

48.64

converted into gehlenite hornfels. Sample 21 was selected from the larg-
Pwo

est paralava cluster (of about 30× 20 m) in a totally carbonated matrix

2

from the middle of the section at a depth of about 20–25 m. There the
0.994
0.001
0.001
1.002
0.00
0.03
0.03

0.04

0.03
0.00
51.43

48.37

99.97

paralavas are branching and have been most often highly altered in
Pwo

their apices but are fresh where they widen to 15–35 cm. The paralava
1

clusters are spaced at 25 m and mark individual foci of gas combustion

Analysis no.

and CM-related local melting.

Mineral

The paralavas are massive rock of deep greenish-brown color.

Al2O3
Table 2

Na2O

Total
MnO
MgO

P2O5
TiO2
SiO2

CaO

Their textures vary within a single vein from fine- to relatively

FeO

Mg
Ca
Fe
Si

coarse-grained holocrystalline consisting of up to 1 cm (sample 21)

80 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90

Fig. 3. Typical view of the Nabi Musa dome paralavas. (a, b) Rootless paralava veins. Vein swelling is determined by the encounter of a nearly vertical vein with a breccia zone ([a]
and [b] correspond to samples 21 and 12, respectively); (c, d) Appearance of paralava samples YV-197 (c) and 12 (d); retrograde Cr+ 6-bearing ettringite (canary yellow) and afwil-
lite (white) fill vesicles in the melted rocks.

parawollastonite and 2 mm (sample 12D) rankinite. The paralava have abnormally high ratios (~ 1.3) of CaO (48.10–51.00 wt.%) to
surfaces are strongly altered and reworked into a fibrous aggregate SiO2 (35.00–38.50 wt.%). The paralava mineral assemblage consists
of tobermorite (10.6 and 11.3 Å) with ettringite and afwillite. Sporadic of (vol.%) 50–70 rankinite; 20–30 melilite; ~10 pseudowollastonite;
vesicles are filled with aggregates of calcite and calcium silicate hy- b5 wollastonite; ~2–3 fluorapatite; b5 Ti-rich andradite; b5 cuspi-
drates (Fig. 3c). dine; ~ 2 larnite; ~ 2 nagelschmidtite. The paralava samples are mainly
The Nabi Musa paralavas are remarkable in their chemistry contain- composed of a mosaic of subhedral rankinite crystals (up to 1–2 mm
ing 85 to 91 wt.% CaO and SiO2 while the presence of other major oxides in size) and pseudowollastonite laths (600–900 μm) and contain a
(except for phosphorus) is notably lower than in any paralavas studied few compact domains rich in poikilitic melilite crystals (Fig. 4a,b).
before (Table 1). Water and CO2 contents in samples depend on the The melilites are of two types: (i) abundant large squarish, euhedral,
depth of their retrograde alteration and on the ratios of newly formed and rarely long-prismatic crystals (up to 1 mm), of diverse and vari-
calcite to CSHs. The paralava parent rocks were reconstructed as a able colors, with their cores stuffed with larnite, rankinite, and pseu-
mixture of Upper Cretaceous marine carbonates and marl and Early dowollastonite inclusions (Fig. 4b,c) or (ii) yellow squarish crystals
Cretaceous Nubian sandstone (Sokol et al., 2010). (up to 250 μm) enclosed in rankinite. The irregularly-shaped spaces
Samples 12C, 12D, and YV-197 have similar bulk chemistry and between pseudowollastonite and rankinite crystals are filled with
mineral compositions (Tables 1, 4). They are larnite-normative and honey-yellow ferrigehlenite, single wollastonite laths, and reddish-
brown Ti-rich andradite (Fig. 4a,d,e,f). Nagelschmidtite was found as
oval inclusions (5–10 μm in diameter) in rankinite and very rare in
Table 3
Crystallographic and experimental data for natural CaSiO3 polymorphs. pseudowollastonite (Figs. 4a, 5a,b). It looks like specific cloudy gray-
ish turbid matter with a shagreen surface. Commonly nagelschmidtite
Wollastonite Pseudowollastonite
inclusions are partially decomposed, hydrated and converted into cal-
a (Å) 7.9285(4) 6.83556(10) cium silicate hydrate. The interstitial space between melilites is filled
b (Å) 7.3234(3) 11.86962(18) with bead-like trails (300–400 μm) of Ti-rich garnet grains buried in
c (Å) 7.0684(4) 19.6255(3)
α (°) 90.077(4) 90
cuspidine matrix (Fig. 4f). Garnets, which either build up skeletal aggre-
β (°) 95.201(5) 90.6805(13) gates or form interstitial patches, are typical quenching forms. Rankinite,
γ (°) 103.399(4) 90 pseudowollastonite, and fluorapatite share same oval melt inclusions
V (Å3) 397.50(3) 1592.21(4) (5–170 μm) of brown partially devitrified glass (Fig. 5a,b). Occasionally
Z 6 24
wollastonite contains trails of small (2–10 μm) melt inclusions (Fig. 4e).
Space group P1 C2/c
d (g/cm3) 2.912 2.908 Paralava sample 21 contains almost equal percentages of CaO and
μ (MoKα) (mm− 1) 2.562 2.559 SiO2 (44.3 and 46.5 wt.%, respectively; CaO/SiO2 ratio about 1,
2θ range (°) 5.30–56.60 4.14–74.00 Table 1). The rock consists of lath-like abundant (75–90 vol.%) para-
Number of Ihkl measured 13,114 32,792 wollastonites (form 100 μm up to 1 cm in size) and minor short-
Number of unique F2hkl 1508 4017
Rint 0.0111 0.0390
prismatic melilites (8–15 vol.%), sporadic wollastonite crystals (up
Number of observed reflections [I > 2σ(Ι)] 1419 3328 to 5 vol.%), and fluorellestadite “pencils” (up to 3 vol.%) (Fig. 6). Pseu-
Number of variables 137 140 dowollastonites have never been unambiguously distinguished in
R1, wR2 for observed reflections [I > 2σ(Ι)] 0.0179, 0.0468 0.0290, 0.0612 thin laths, but the mineral was identified as subordinate phase by
R1, wR2 for all data 0.0196, 0.0479 0.0410, 0.0653
means of X-ray powder diffraction (of about 5–10% relative to para-
Residual electron density (e/Å3) 0.419, − 0.288 0.527, − 0.358
wollastonite content). Ti-rich garnets occur commonly as subhedral
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90 81

Table 4 grains or irregular interstitial patches. Occasionally these are partly

Mineral assemblages in paralavas from Nabi Musa dome (results from light and SEM faceted grains (up to 0.5 mm) that host numerous small euhedral
microscopy, XRPD, EPMA and TG-DTA data).
melilites and fluorellestadite or stuffed with nagelschmidtite “tu-
Mineral Formula Sample bules” (Fig. 6e,f). Interstices of coarse parawollastonite contain spo-
12C 12D YV- 21 radic grains of wollastonite (up to 500 μm) and anhedral cuspidine
197 (100–300 μm). Sometimes the growth zones of parawollastonite
Rankinite Ca3[Si2O7] – grains are decorated with numerous small melt inclusions with fluid
Melilite Ca2(Al,Fe)[(Si,Al)2O7] ●●● ●●● ●●● ●● bubbles (Fig. 5c).
Parawollastonite β-Ca3Si3O9 (2M) – – –
Pseudowollastonite α-Ca3Si3O9 ●● ●● ●● ●
Wollastonite β-Ca3Si3O9 (1T) ● ● ● ●●
Larnite β-Ca2[SiO4] ● ● ● –
7. CaSiO3 polytypes and polymorphs
Cuspidine Ca4[Si2O7]F2 ● ● ● ●
Nagelschmidtite (Na,K)2 − xCa5 + x(PO4)4 − x ● ● ● ● The studied paralava samples contain three low-pressure modifica-
(SiO4)x tions of CaSiO3. Samples 12D, 12C, and YV-197 bear pairs of coexisting
Fluorapatite Ca10(PO4)6F2 ● ● ● –
pseudowollastonite and wollastonite (Table 4). Abundant parawollasto-
Fluorellestadite Ca10[(PO4),(SO4),(SiO4)]6F2 – – – –
Ti-rich andradite Ca3(Fe,Ti)2[Si3 − x(Fe,Al)xO12] ● ● ● ●● nite accompanied by subordinate wollastonite and pseudowollastonite
Hematite α-Fe2O3 ● ● ● – has been distinguished in sample 21 only. All wollastonite exists as
Ettringite Ca6Al2(SO4)3(OH)12·26H2O ● – ● ● sporadic medium-sized laths separated from large grains of both
Tobermorite Ca5[Si6O16](OH)2·4H2O ● – – ● pseudowollastonite and parawollastonite (Figs. 4d,e, 6a,b,c,d). It is
Calcite CaCO3 ● ● – ●
Barite Ba(SO4) ● ● – –
obviously a late product of melt crystallization. We have found no
petrographic signature of partial reversion of high-temperature CaSiO3
, very abundant; ●●●, abundant; ●●, minor; ●, very minor; –, absent.
modifications to wollastonite or its rims around the pseudowollastonite
or parawollastonite cores. At the same time, single-crystal X-ray

Fig. 4. Photomicrographs of Nabi Musa paralava (sample 12D).(a) Mosaic of subhedral rankinite with numerous melt inclusions. Interstices are filled with melilite and Ti-andradite (plane-
polarized light);(b) Local areas of paralava enriched by poikilitic crystals of buff or leather-brown melilite hosted larnite (plane-polarized light);(c) Light-colored squarish gehlenite crystals
embayed in rankinite and surrounded by radiating cracks (plane-polarized light);(d) Subordinate pseudowollastonite plates (cross-polarized light);(e) Occasionally wollastonite is full by trails
of small “smoky” melt inclusions with fluid bubble, probably representing resealed fractures, and lack in any mineral inclusions (plane-polarized light);(f) Beaded trails of Ti-andradite grains
buried in a cuspidine matrix (plane-polarized light). Csp = cuspidine, Grt = garnet (Ti-andradite), Mel = melilite, Pwo = pseudowollastonite, Rnk = rankinite, Wo = wollastonite.
82 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90
Fig. 5. Primary melts inclusions in paralava minerals.(a) Unheated inclusions in rankinite
containing brownish glass, larnite, nagelschmidtite, fluorapatite and opaque minerals (sam-
ple 12D) (plane-polarized light);(b) Heated at 1320 °C and then quenched inclusions in
rankinite composed of greenish glass and nagelschmidtite (sample 12D) (plane-polarized
light);(c) Unheated small melt inclusions with fluid bubble in parawollastonite (sample
21) (plane-polarized light). Gl = glass, Grt = garnet (Ti-andradite), Lrn = larnite, Mel =
melilite, Nag = nagelschmidtite, Prw = parawollastonite, Rnk = rankinite.
experiments show that at least some parawollastonites are epitaxial in-
tergrowths of wollastonite-lT.
Wollastonite occurs as isolated lath-like crystals, often twinned,
elongated in the c direction with perfect {100} and good {102} and
{001} cleavages; the mineral is biaxial with (−) 2 V ≈ 40° and negative
elongation. Pseudowollastonite shows typical polysynthetic twinning
and distinct cross-cleavage parallel to the planes {100} and {001}. In
thin sections pseudowollastonite appears colorless or bluish. It has bire-
fringence higher than wollastonite, is uniaxial, positive, rarely biaxial,
with (+) 2 V ≈ 0° and negative elongation. Unlike wollastonite and
parawollastonite which have a faint bluish glow, pseudowollastonite
gives distinct lilac fluorescence in the electron beam. Parawollastonite
is easy to spot in thin sections due to its grayish-pink color in plane-
polarized transmitted light, bright colors (from orange to violet) in
cross-polarized light, and a distinct to perfect {100}, {102} and {001}
cross-cleavage (Fig. 6b,d). It is biaxial with (−) 2 V ≈ 40°. All CaSiO3
modifications are highly resistant to alkaline hydrothermal alteration;
they have survived corrosion and are free from tobermorite and ettringite
replacement. Pseudowollastonite, parawollastonite, and wollastonite
from the Nabi Musa paralavas are fairly pure CaSiO3 (Table 2). So all an-
alyzed CaSiO3 modifications form Nabi Musa paralavas are poorer in
MgO and FeO, than CaSiO3 modifications in both sanidinite facies haloes
and igneous melilitolite (Grapes, 2011; Melluso et al., 2003; Reverdatto,
1973; Stoppa and Sharygin, 2009).
The pseudowollastonite we studied belongs to the most wide-
spread four-layer polytype: a = 6.83556(10) Å, b = 11.86962(18) Å,
c = 19.6255(3) Å, β = 90.6805(13)°, V = 1592.21(4) Å 3, space group
C2/c. The atomic coordinates and displacement parameters are
given in Table 5. The structural data are deposited as CIF at the ICSD
(CSD No.423129). The crystal structure of natural pseudowollastonite
is close to that of a synthesized sample, a = 6.8394(5) Å, b = 11.8704
(9) Å, c = 19.6313(9) Å, β = 90.667(6)°, V = 1593.7(2) Å 3, space
group C2/c (Yang and Prewitt, 1999a). Interatomic distances and
Si\O\Si angles comparative with ones of synthetic sample are
shown in Table 6. The results of two different experiments are similar
within the limits of the experimental errors.
The investigated wollastonite is a common 1T polytype: a = 7.9285
(4) Å, b = 7.3234(3) Å, c = 7.0684(4) Å, α = 90.077(4)°, β = 95.201
(5)°, γ = 103.399(4)°, V = 397.50(3) Å3, space group P1 (Table 3).
We failed to find a single crystal of parawollastonite (2M wollas-
tonite), and for this reason parawollastonite selected for the single-
crystal experiment was an epitaxial intergrowth with wollastonite
at the ratio close to 1:1. Eventually, we had to confine ourselves to de-
termining the unit cell parameters: a = 15.4268(16) Å; b = 7.3239(9)
Å; c = 7.0693(8) Å; β = 95.378(10)°; V = 795.20(11) Å 3.
8. Chemistry and diagnostic features of associated minerals
The melilite compositions should be attributed to the solid solution
of gehlenite (Ca2Al2SiO7) (34.63–68.54 mol%), ferrigehlenite Ca2(Fe 3 +2
SiO7) (3.70–21.78) and akermanite Ca2(MgSi2O7) (15.00–28.86 mol%);
they exhibit a narrow range with respect to ferro-akermanite Ca2
(Fe 2 +Si2O7 mol%) (3.41–8.23) (Table 7, Fig. 7a). Total K2O content
is below 0.35 wt.%. Na2O concentration is commonly under 0.88 wt.%,
however the crystal rims are relatively rich in soda-melilite (up to
3.16 wt.% Na2O). Melilite crystals have atomic Mg/(Mg + Fe) that varies
from 0.44 to 0.63. Thus the major compositional variability in these
melilites mainly involves Fe3 + → Al3 + substitution with little variabili-
ty in Si, Mg, or Ca. Many large melilite crystals typically show both opti-
cal and chemical zoning. In thin sections the color varies from yellow
and straw-yellow for the gehlenite-rich variety to buff and leather-
brown for the ferrigehlenite variety (Fig. 4b). Small squarish straw meli-
lites hosted by rankinite are richest in Ca2Al2SiO7 (64.25–68.54 mol%).
The Nabi Musa melilites are very close to the majority of the Mottled
Zone CM melilites (Gross, 1977; Sokol et al., 2008). They are also similar
to melilites from Italian melilitolites (Melluso et al., 2003; Stoppa and
Sharygin, 2009) and to those in coal-fire buchite from Wyoming
(USA), (Foit et al., 1987), with the only difference that the Nabi Musa
varieties contain less akermanite than the former and less ferrigehlenite
than the latter.
Rankinite is a very rare mineral that has been found recently in
natural melt rocks. It is a rock-forming mineral in Ca-rich and Si-
depleted paralavas from the Hatrurim Basin (Sokol et al., 2008) and
an accessory in melilitolites from Colle Fabbri (Stoppa and Sharygin,
2009). Euhedral prismatic rankinite is the earliest phase in the Nabi
Musa pseudowollastonite-bearing paralavas (Fig. 4a). It has no visible
cleavage, is colorless or shows different pink hues in thin section
(without any evidence of chemical alteration in the pink zones),
and has a faint lavender fluorescence under the electron beam. Its
composition matches well pure Ca3[Si2O7] (Table 8). A special effort to
find the orthorombic polymorph of Ca3[Si2O7]-kilhoanite has failed. In
highly altered paralavas, rankinite is usually replaced by tobermorite.
The unit-cell parameters of rankinite determined by X-ray single-
crystal analysis are: a = 10.5806(2) Å; b = 8.90679(10) Å; c = 7.87952
(16) Å; β = 119.589(3)°; V = 645.73(3) Å3.
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90 83

Fig. 6. Photomicrographs showing paragenetic relationship of minerals in Nabi Musa paralava sample 21.(a) Interstices of coarse-grained parawollastonite contain sporadic grains of meli-
lite, Ti-andradite, and wollastonite (plane-polarized light);(b) Parawollastonite individual and wollastonite plate (cross-polarized light);(c, d) Distinctive optical and morphological fea-
tures of parawollastonite versus wollastonite (plane-polarized and cross-polarized light, respectively);(e) Melilite squarish crystals buried in Ti-andradite (plane-polarized light);(f)
Tubular inclusions of altered turbid nagelschmidtite in Ti-andradite (plane-polarized light). Ell-(F) = fluorellestadite, Grt = garnet (Ti-andradite), Mel = melilite, Prw = parawollastonite,
Rnk = rankinite, Wo = wollastonite.

Specific minerals such as larnite and nagelschmidtite were men- coal Basin, Czech Republic (Žáček et al., 2005). In thin sections of
tioned as rare accessory constituents in extremely Ca-rich paralavas the Nabi Musa paralavas, fresh larnite appears colorless. The X-ray
from the Hatrurim Basin (Grapes, 2011; Sokol et al., 2008). Larnite powder pattern of larnite is identical with those of β-Ca2[SiO4] (PDF
was found in melilite paralavas from the North Bohemian brown- card 33-302). According to Bredig (1943) and Morey (1963), β-Ca2

Table 5
Atomic positional coordinates and displacement parameters (Å) for pseudowollastonite.

Atom x y z U11 U22 U33 U12 U13 U23

Ca1 0 0 0 0.01309(15) 0.01008(15) 0.00812(14) 0.00418(11) 0.00093(11) 0.00120(11)

Ca2 0 0.34269(3) 0.25 0.01180(14) 0.00765(14) 0.00786(14) 0 0.00140(10) 0
Ca3 0 0.32896(3) 0.75 0.00714(13) 0.01540(16) 0.00802(14) 0 − 0.00032(10) 0
Ca4 0 0.00448(3) 0.75 0.01026(14) 0.00850(14) 0.00740(14) 0 0.00032(10) 0
Ca5 0.01122(3) 0.33571(2) 0.000464(12) 0.00892(10) 0.00997(10) 0.00752(10) − 0.00142(8) 0.00043(7) − 0.00043(7)
Si1 0.29303(5) 0.03890(3) 0.375037(17) 0.00749(14) 0.00693(14) 0.00579(13) 0.00082(10) − 0.00009(10) − 0.00023(10)
Si2 0.09278(5) 0.17031(3) 0.127899(17) 0.00611(13) 0.00820(14) 0.00587(13) − 0.00012(10) 0.00017(10) 0.00013(10)
Si3 0.29810(5) 0.29718(3) 0.377897(17) 0.00794(14) 0.00666(14) 0.00588(14) − 0.00066(10) 0.00019(10) − 0.00006(10)
O1 0.34745(14) 0.34490(8) 0.45191(5) 0.0146(4) 0.0120(4) 0.0078(4) − 0.0023(3) − 0.0011(3) − 0.0017(3)
O2 0.15487(14) 0.48795(8) 0.19702(5) 0.0158(4) 0.0123(4) 0.0077(4) − 0.0026(3) 0.0014(3) 0.0023(3)
O3 0.19045(14) 0.17213(8) 0.20202(5) 0.0113(4) 0.0159(4) 0.0078(4) 0.0008(3) − 0.0022(3) 0.0001(3)
O4 0.05634(13) 0.28089(8) 0.37485(5) 0.0075(4) 0.0079(4) 0.0148(4) − 0.0002(3) − 0.0004(3) − 0.0005(3)
O5 0.20079(14) 0.17030(9) 0.05692(5) 0.0117(4) 0.0192(5) 0.0084(4) 0.0006(3) 0.0034(3) 0.0013(3)
O6 0.05207(13) 0.05802(8) 0.37383(5) 0.0071(3) 0.0081(4) 0.0149(4) 0.0002(3) − 0.0001(3) − 0.0002(3)
O7 0.35422(14) 0.35114(8) 0.30691(5) 0.0168(4) 0.0126(4) 0.0088(4) − 0.0036(3) 0.0018(3) 0.0020(3)
O8 0.15807(14) 0.48531(8) 0.05277(5) 0.0158(4) 0.0134(4) 0.0078(4) − 0.0029(3) − 0.0008(3) − 0.0023(3)
O9 0.38925(13) 0.16732(7) 0.37621(5) 0.0084(3) 0.0075(4) 0.0145(4) − 0.0004(3) − 0.0003(3) 0.0000(3)
84 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90

Table 6 almost invariable concentrations of CaO (59.64–60.72), SiO2

Selected interatomic distances (Å) and Si–O–Si angles (°) in natural pseudowollasto- (27.93–30.73), and P2O5 (5.49–7.93), in wt.% (Table 8). Regular presence
nite in comparison with synthetic sample (Yang and Prewitt, 1999a).
of K2O (1.01–1.53 wt.%) and Na2O (1.02–1.89 wt.%) is in agreement with
Natural Synthetic Natural Synthetic the composition of the synthetic compound (Na,K)2 − xCa5 + x(PO4)4 − x
sample sample sample sample (SiO4)x. A double substitution mechanism, Na+ + P+ 5 →Ca2 + + Si4 +
Ca1-O1(2×) 2.3117(9) 2.311(1) Si1-O2 1.5825(10) 1.585(1) can be realized under the temperature above 1200 °C, where a solid so-
Ca1-O5(2×) 2.6797(10) 2.680(1) Si1-O6 1.6626(9) 1.662(1) lution with α-NaCaPO4 and α-Ca2[SiO4] is stable (Rivenet et al., 2000).
Ca1-O6(2×) 2.5987(10) 2.600(1) Si1-O8 1.5850(10) 1.585(1)
Both compounds have a glaserite-type structure NaK3(SO4)2, the fact
Ca1-O8(2×) 2.5736(10) 2.575(1) Si1-O9 1.6602(9) 1.661(1)
Mean 2.5409 2.542 Mean 1.6226 1.623 that explains notable potassium and SO3 (0.11–0.28 wt.%) contents in
Ca2-O2(2×) 2.2805(10) 2.282(1) Si2-O3 1.5934(10) 1.595(1) natural nagelschmidtite.
Ca2-O3(2×) 2.5902(10) 2.589(1) Si2-O4 1.6623(9) 1.664(1) Cuspidine is a common minor mineral of all analyzed paralavas
Ca2-O7(2×) 2.6563(10) 2.584(1) Si2-O5 1.5843(10) 1.584(1) that fills intergranular space and is closely associated with Ti-rich gar-
Ca2-O4(2×) 2.5822(9) 2.658(1) Si2-O6 1.6604(10) 1.663(1)
net (Fig. 4f). The mineral is colorless, void of distinct cleavage, is char-
Mean 2.5273 2.528 Mean 1.6251 1.627
Ca3-O2(2×) 2.6365(10) 2.633(1) Si3-O1 1.5915(10) 1.594(1) acterized by moderate relief and birefringence, and fluoresces faintly
Ca3-O3(2×) 2.3058(9) 2.307(1) Si3-O4 1.6642(9) 1.663(1) by lavender color under the electron beam. Its composition corre-
Ca3-O7(2×) 2.6147(11) 2.613(1) Si3-O7 1.5845(10) 1.585(1) sponds to stoichiometric Ca4[Si2O7]F2. Fluorine varies from 10.05 to
Ca3-O9(2×) 2.5991(10) 2.601(1) Si3-O9 1.6630(9) 1.662(1)
10.60 wt.%, which approaches its maximal content in the mineral
Mean 2.5390 2.539 Mean 1.6258 1.626
Ca4-O7(2×) 2.2813(10) 2.569(1) Si2-O4-Si3 134.52(6) 134.53 (Table 9).
Ca4-O6(2×) 2.5617(9) 2.649(1) Si1-O6-Si2 134.45(6) 134.39 Ti–rich andradite is a typical late phase which sometimes displays
Ca4-O2(2×) 2.5684(10) 2.562(1) Si1-O9-Si3 134.65(6) 134.55 signature of quenching textures (Figs. 4a,f, 6e,f). The ranges of oxide con-
Ca4-O3(2×) 2.6467(10) 2.282(1) Mean 134.54 134.49 centrations in subhedral garnet grains from sample 21 (in wt.%) are as
Mean 2.5145 2.516
follows: CaO (33.10–33.28), SiO2 (29.47–30.10), Fe2O3 (25.88–26.95),
Ca5-O1 2.6365(10) 2.637(1)
Ca5-O1′ 2.5946(10) 2.598(1) TiO2 (6.96–7.59), Al2O3 (1.91–2.20), Cr2O3 (0.62–0.77), ZrO2 (0.44–
Ca5-O4 2.5790(10) 2.578(1) 0.48) (Table 10). The garnet compositions show good positive correla-
Ca5-O5 2.5937(10) 2.594(1) tion between Ti and Cr. Garnet skeletal aggregates and interstitial
Ca5-O5′ 2.2806(10) 2.282(1)
patches (paralava 12D) have the highest TiO2 (9.72–10.69 wt.%) and
Ca5-O8 2.2782(10) 2.280(1)
Ca5-O8′ 2.6297(10) 2.629(1)
V2O5 (0.23 wt.%) enrichments but are depleted in Cr2O3 (≤0.37 wt.%).
Ca5-O9 2.5679(10) 2.568(1) These garnets show marked negative correlation between Si and Ti con-
Mean 2.5200 2.521 tents. Si, Al, Ca decrease and Ti, Cr and Fe increase distinctly toward the
top of bead-like trails of garnet grains. All Ti-rich garnets from the Nabi
Musa paralavas are low in Si (SiO2 26.39–27.58 wt.%). The unit-cell pa-
[SiO4] can survive at low temperatures only in the presence of stabi- rameters of Ti-rich andradite (paralava 12D) determined by X-ray
lizers, among which the main one is phosphorus. Larnite from para- single-crystal analysis are: a =12.1577(7) Å, V =1797.0(3) Å3.
lava 12D contains 1.5–1.8 wt.% P2O5. Minerals of the fluorapatite–fluorellestadite joint are relatively
Nagelschmidtite of oval inclusions in rankinite is fresh, fluoresces abundant early crystallizing phases in the Nabi Musa paralavas which
markedly bluish under the electron beam, and shows distinct poly- occur as single “pencil-like” long-prismatic or acicular crystals up to
synthetic twinning structures (Figs. 4a, 5a,b). Nagelschmidtite has 0.5 mm across as inclusions in Ti-rich garnet, melilite, and rankinite

Table 7
Representative analyses of melilites from Nabi Musa paralavas.

Sample 12D 21

c r c m m r c c r

SiO2 28.87 28.90 29.17 29.42 29.49 29.62 34.57 33.52 35.67
Al2O3 24.47 26.36 23.50 21.49 20.41 19.34 15.74 16.42 15.53
Fe2O3 2.27 1.07 2.91 3.76 4.91 6.04 5.02 5.75 4.03
FeO 0.85 2.14 1.73 1.96 2.08 1.84 1.13 1.61 1.24
MgO 2.80 2.22 2.96 3.20 3.17 3.20 3.97 3.91 4.07
CaO 38.85 38.91 38.26 38.14 37.98 37.60 35.45 35.09 34.76
Na2O 0.85 0.88 0.84 0.74 0.74 0.85 2.71 2.40 3.16
K2O 0.25 0.25 0.28 0.24 0.29 0.29 0.27 0.35 0.27
P2O5 0.00 0.01 0.04 0.00 0.01 0.03 0.00 0.00 0.00
Total 99.24 100.75 99.68 99.00 99.13 98.87 98.85 99.07 98.80
Si 1.337 1.318 1.351 1.379 1.388 1.392 1.610 1.565 1.653
Al 1.336 1.417 1.283 1.188 1.132 1.089 0.864 0.904 0.848
Fe3 + 0.079 0.037 0.102 0.133 0.174 0.217 0.176 0.202 0.141
Fe2 + 0.033 0.082 0.067 0.077 0.082 0.073 0.044 0.063 0.048
Mg 0.193 0.151 0.204 0.224 0.222 0.228 0.276 0.272 0.281
Ca 1.929 1.902 1.899 1.916 1.915 1.900 1.769 1.756 1.726
Na 0.076 0.078 0.075 0.067 0.068 0.079 0.245 0.217 0.284
K 0.015 0.014 0.017 0.014 0.017 0.018 0.016 0.021 0.016
NaCaAlSi2O7 4.51 4.64 4.61 4.08 4.25 4.82 12.84 11.93 14.79
Ca2Fe3 +2SiO7 8.10 3.70 10.07 13.36 17.54 21.78 18.13 20.16 14.65
Ca2FeSi2O7 3.41 8.13 6.67 7.74 8.23 7.50 4.53 6.25 4.97
Ca2MgSi2O7 19.73 15.00 20.24 22.31 22.22 22.68 28.42 27.03 28.86
Ca2Al2SiO7 64.25 68.54 58.41 52.50 47.75 43.22 36.09 34.63 36.72

FeO and Fe2O3 calculated from mineral stoichiometry.

c = core.
r = rim.
m = middle.
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90
Fig. 7. Triangular diagrams showing the composition fields of Nabi Musa melilite, fluor-
apatite and fluorellestadite.(a) Compositions of melilite from paralavas compared with
the composition field of metamorphic melilites. Classification diagram for melilites is
from Melluso et al. (2003);(b) Phosphorus-rich part of the Si–P–S diagram showing
composition trend of fluorellestadite and fluorapatite from Nabi Musa paralavas.
Most of the points are shifted toward the P–Si-side.Sample 13 (paralava from Nabi
Musa, unpublished data of the authors): larnite, melilite, cuspidine, fluorellestadite,
opaque minerals.
(Fig. 6c). Rarely fluorapatite is found in cuspidine or in the interstitial
space between pseudowollastonite and garnet. The minerals look similar,
colorless or grayish. Fluorapatite has little variable CaO
(57.79–58.56 wt.%) but a relatively broad range (in wt.%) of P2O5
(29.28–32.78), SO3 (3.25–4.90), and SiO2 (4.10–5.04). The mineral gener-
ally contains 2.67–3.27 wt.% of F, and less Cl (b 0.01 wt.%) (Table 9). The
concentrations of P, S, Si, and F vary slightly from core to rim. The concen-
trations of Al2O3, MnO, BaO, SrO, Na2O, and K2O impurities are generally
low, and FeO varies from 0.01 to 0.27 wt.%.
Fluorellestadite contains slightly lower CaO (56.16–56.71 wt.%),
and markedly higher SiO2 (10.87–11.03 wt.%) and SO3 (10.91–
12.94 wt.%) than in fluorapatite, F up to 3.06 wt.%, and low P2O5
(16.72–19.44 wt.%) (Table 9). The contents of impurities are similar
to those in fluorapatite. Zoning in P, S, Si, and F is fuzzy. Fluorellestadite
compositions plotted on the Si–P–S triangle (Fig. 7b) obviously show a
shift from the stoichiometry line toward the silica corner. Fluorellestadite
X-ray powder patterns wholly resemble those of PDF card 450009.
9. Discussion
The very low probability for the origin and survival of pseudowol-
lastonite in igneous rocks has been positively proven. Its appearance
in natural environments is limited by two basic factors: the scarcity
85
of larnite-normative melts and the high concentrations of Mg and
Fe, besides Ca, in wollastonite-bearing rocks which are most often
high-temperature melilite varieties (Deer et al., 1997; Longhi,
1987). The latter crystallochemical reason for the scarcity of natural
pseudowollastonite consists more specifically in the fact that wollas-
tonite is stabilized with respect to pseudowollastonite by preferential
substitution of Mg 2 +, Fe 2 +, and Mn 2 + in low-temperature CaSiO3
structures. The subsolidus conversion of pseudowollastonite to wol-
lastonite solid solution is effectuated by dissolving the former in the
melt (Deer et al., 1997; Longhi, 1987; Morey, 1963; Osborn and
Schairer, 1941; Rietmeijer, 1999; Scott et al., 1986; Shinno, 1970).
Pseudowollastonite may be expected to occur in paralava, a low-
pressure melt rock of non-igneous origin, as it bears free Ca much
more often than magmas. However, the vast majority of ultrahigh-
temperature paralavas (T > 1150 °C) likewise contain wollastonite in-
stead of pseudowollastonite.
9.1. Storage capacity of pseudowollastonite, wollastonite, and bustamite
structures
At ambient pressure, stoichiometric wollastonite is stable only
below 1125° ± 10 °C (Osborn and Schairer, 1941) but can rise up to
1610 °C at 23 kbar (Kushiro, 1964). In the case of both CM melts
and Colle Fabbri melilitites that crystallized near the ground surface,
the effect of pressure is obviously negligible. Pressure being constant,
the temperature of wollastonite → pseudowollastonite inversion de-
pends mainly on chemistry of both minerals. The reversion tempera-
ture is raised very considerably by the metasilicate solid solutions,
namely CaSiO3–CaMgSi2O6 and CaSiO3–CaFeSi2O6. Wollastonite dis-
solves up to about 10 mol% of MgSiO3 and FeSiO3, while pseudowol-
lastonite is a stoichiometric CaSiO3 compound (Deer et al., 1997;
Grapes, 2011; Morey, 1963; Osborn and Schairer, 1941).
The crystallochemical reason behind this fact is as follows. The Ca–
O distances in the wollastonite structure lie within the interval
2.21–2.64 Å, with a mean about 2.40 Å (Ohashi, 1984). Although the
Fe 2 +, Mn 2 +, and Mg 2 + cations have their sizes substantially smaller
than Ca 2 + at the subsolidus, both stable and metastable solid solu-
tions can exist in the systems CaSiO3–CaMgSi2O6, CaSiO3–CaFeSi2O6,
and CaSiO3–MnSiO3. At high temperatures, the (Ca,Fe)SiO3 solid solu-
tions contain up to 76 wt.% FeSiO3. The wollastonite structure can in-
corporate and retain only limited amounts of either Fe 2 + (up to
12 mol% FeSiO3) or Mn 2 + (up to ~ 25 mol% MnSiO3). Compositions
containing more than ~ 10% (Fe,Mn)SiO3 crystallize with the busta-
mite or pyroxmangite structure (Deer et al., 1997). In the system
CaSiO3–CaMgSi2O6, the wollastonite structural type appears over
the whole range of compositions. However, wollastonite was synthe-
sized stably within the limited series between Wo100 and Wo85,
though the compositions richer in the CaMgSi2O6 component are
metastable over the whole temperature range (Shinno, 1970).
In the pseudowollastonite structure, Ca-polyhedra are expanded
slightly in comparison with wollastonite; the Ca–O distances lie with-
in the interval 2.28–2.64 Å, and the mean volume is equal to 2.53 Å
(Yamanaka and Mori, 1981; Yang and Prewitt, 1999a, 1999b). The
larger sizes of cation polyhedra restrict considerably the possibility
of their occupation by smaller cations such as Fe 2 + and Mg 2 +. So
both synthetic and natural pseudowollastonites correspond to pure
CaSiO3.
The wollastonite structure can accommodate only very limited
amounts of other smaller cations (Al and Ti). No appreciable solid so-
lutions exist between both pseudowollastonite/wollastonite–melilite
and pseudowollastonite/wollastonite–anorthite pairs (Deer et al.,
1997; Longhi, 1987; Morey, 1963). Pseudowollastonite forms binary
eutectics (saddle points) with akermanite at 1402 °C, gehlenite at
1310 °C, and anorthite at 1292 °C. Natural non-stoichiometric Ti(±Al)-
Mg-wollastonites complicated by coupled substitution (CaTiAl2O6) was
identified only in rapidly heated and quenched products of dynamic
86 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90

Table 8
Representative analyses of nagelschmidtite and rankinite from CM rocks of the Mottled Zone, Israel.

Mineral Nagelschmidtite Rankinite

Analysis no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Host mineral Rnk Rnk Rnk Rnk Rnk Rnk Rnk Rnk Ti-Adr Ti-Adr

SiO2 28.86 28.60 28.39 28.02 27.99 27.93 29.30 30.73 27.74 27.39 27.88 41.29 41.99 41.55 41.61 41.63
TiO2 0.03 0.02 0.00 0.00 0.00 0.00 0.02 0.00 0.03 0.01 0.02 0.00 0.05 0.04 0.01
Al2O3 0.19 0.20 0.16 0.03 0.13 0.21 0.23 0.19 0.00 0.04 0.03 0.01 0.03 0.01 0.03 0.00
FeO 0.04 0.06 0.12 0.05 0.08 0.13 0.57 1.20 0.30 0.20 0.02 0.12 0.10 0.07 0.07 0.24
MgO 0.41 0.15 0.10 0.10 0.16 0.15 0.56 0.41 0.29 0.10 0.05 0.18 0.00 0.00 0.00 0.23
CaO 59.68 60.12 60.24 59.70 60.72 59.84 60.20 59.64 57.82 58.10 62.06 58.30 57.69 58.04 58.04 32.55
Na2O 1.41 1.51 1.36 1.89 1.33 2.16 1.02 1.09 1.71 2.24 0.82 0.04 0.02 0.00 0.06 0.11
K2O 1.45 1.48 1.53 1.50 1.01 1.17 0.60 0.88 3.33 2.77 0.84 0.00 0.01 0.01 0.00 0.00
P2O5 6.80 6.75 7.12 7.93 7.41 7.25 6.36 5.49 8.42 8.80 8.27 0.10 0.08 0.07 0.11
SO3 0.23 0.23 0.18 0.11 0.28 0.27 0.13 0.25 0.12 0.12 0.12
Total 99.10 99.12 99.19 99.35 99.13 99.11 98.98 99.89 99.94 99.87 100.09 100.08 99.92 99.80 99.98 99.83
Cations calculated on the basis of 4 oxygens Cations calculated on the basis of 7 oxygens
Si 0.825 0.820 0.813 0.800 0.801 0.801 0.837 0.871 0.792 0.781 0.788 1.979 2.018 1.999 1.998 2.001
Ti 0.001 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.000 0.000
Al 0.006 0.007 0.005 0.001 0.004 0.007 0.008 0.006 0.000 0.001 0.001
Fe 0.001 0.002 0.003 0.001 0.002 0.003 0.014 0.028 0.007 0.005 0.000
Mg 0.018 0.007 0.004 0.004 0.007 0.006 0.024 0.017 0.012 0.004 0.002 0.013 0.000 0.000 0.000 0.006
Ca 1.829 1.847 1.849 1.826 1.861 1.839 1.843 1.811 1.769 1.775 1.880 2.994 2.971 2.992 2.986 2.974
Na 0.078 0.084 0.076 0.105 0.074 0.120 0.057 0.060 0.095 0.124 0.045 0.003 0.002 0.000 0.005 0.010
K 0.053 0.054 0.056 0.055 0.037 0.043 0.022 0.032 0.121 0.101 0.030 0.000 0.000 0.001 0.000 0.000
P 0.165 0.164 0.173 0.192 0.179 0.176 0.154 0.132 0.203 0.212 0.198 0.004 0.003 0.003 0.004 41.63
S 0.005 0.005 0.004 0.002 0.006 0.006 0.003 0.005 0.003 0.003 0.003

1–8, 12–16 = paralava from the Nabi Musa dome, sample 12D.
1–6 = oval unheated inclusions of nagelschmidtite; 7–8 = oval heated inclusion of nagelschmidtite.
9–10, 16 = paralava from the Hatrurim Basin, data from Sokol et al. (2008); 9–10 = tubular inclusions of nagelschmidtite.
11 = melilite–nagelschmidtite CM rock from the Hatrurim Basin, data from Gross (1977).
Kls = kalsilite, Mel = melilite, Rnk = rankinite, Ti-Adr = Ti-andradite.

pyrometamorphism, namely in interplanetary dust particles (Rietmeijer, Schairer (1941), Rietmeijer (1999), Scott et al. (1986), and Shinno
1999). (1970). Therefore, in this discussion we limit ourselves to a few
most important postulates. It is reasonable to approach the issue of
9.2. Crystallization paths with participation of wollastonite and crystallization of pseudowollastonite-bearing melt rocks with the
pseudowollastonite highest temperature CM CaSiO3-bearing paralavas of Nabi Musa.
Crystallization of liquids with paralava compositions can be described
Both crystallization and melting paths where wollastonite and in terms of CaO + SiO2 + Al2O3 which make up 94–96 wt.% of the total
pseudowollastonite are involved, in various petrologically significant oxides present (recalculated LOI-free). The system CaO–SiO2–Al2O3
systems, were detailed in Deer et al. (1997), Jung et al. (2005), lacks solid solutions while pseudowollastonite, gehlenite, and anor-
Lindsley et al. (1969), Longhi (1987), Morey (1963), Osborn and thite form eutectics (Fig. 8).
Paralava sample 21 with high percentages of SiO2 and CaO at about
the CaSiO3 stoichiometry was totally melted experimentally at
Table 9
Representative analyses of cuspidine, fluorapatite and fluorellestadite from Nabi Musa 1480 °C and showed the simplest crystallization path of the melt
paralavas. rocks we studied. This paralava composition plots very close to the
CaSiO3 point (Fig. 8a). Theoretically, pseudowollastonite would crystal-
Mineral Cuspidine Fluorapatite Fluorellestadite
lize the earliest within its stability field between 1540 °C and 1310 °C,
Sample 12 21 12 12 21 21
but in the rock, instead, it was parawollastonite (up to 90 vol.%), whereas
c r c c the percentage of pseudowollastonite did not exceed 10 vol.%. As far as
SiO2 32.65 32.58 5.04 4.10 11.03 10.87 rankinite was absent in the rock (it never crystallized), the melt reached
Al2O3 0.00 0.00 0.02 0.00 0.06 0.00
FeO 0.09 0.00 0.01 0.00 0.27 0.08 Table 10
CaO 60.31 60.11 58.56 57.79 56.16 56.71 Representative analyses of Ti-rich andradites from Nabi Musa paralavas.
P2O5 29.28 32.78 19.44 16.72
SO3 0.00 0.04 4.90 3.25 10.91 12.94 Sample 12D 21
F 10.05 10.60 3.27 2.67 2.76 3.06
r m c
Cl 0.05 0.01 0.01
O = F + Cl –4.24 –4.46 –1.38 –1.13 –1.16 –1.29 SiO2 27.10 26.39 27.58 29.47 30.10 30.10
Total 98.91 99.03 99.70 99.48 99.72 99.27 TiO2 10.33 10.69 9.72 7.59 7.54 6.96
Cr2O3 0.37 0.29 0.05 0.77 0.70 0.62
Cations calculated on the basis of 7 Cations calculated on the basis of 10 Ca V2O3 0.19 0.17 0.23 0.00 0.00 0.00
oxygens atoms Al2O3 2.61 2.73 2.83 1.91 2.20 2.20
Si 2.017 2.014 0.802 0.662 1.8690 1.785 Fe2O3 26.38 26.06 25.59 26.95 25.88 26.80
Ca 3.995 3.986 9.999 10.000 9.963 9.989 MnO 0.06 0.04 0.04 0.04 0.00 0.00
P 0.020 0.002 3.947 4.478 2.723 2.325 CaO 32.76 32.91 32.80 33.28 33.10 33.10
S 0.000 0.002 0.586 0.394 1.355 1.595 ZrO2 0.41 0.47 0.39 0.48 0.46 0.44
F 1.963 2.073 1.647 1.363 1.444 1.159 Total 100.32 99.84 99.30 100.53 100.20 100.47
Cl 0.001 0.004
c = core.
c = core. r = rim.
r = rim. m = middle.
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90 87

(36 wt.%) and three times more Al2O3 (6 wt.%) than sample 21. Pro-
jected into the system CaO–SiO2–Al2O3, it falls within the crystalliza-
tion field of larnite (Fig. 8b). Diverse textural relations between
rock-forming and subordinated minerals as a record of the complex
crystallization path of this paralava are illustrated in Fig. 4. Theoreti-
cally, crystallization begins with larnite (~1520–1400 °C) and ranki-
nite (Ca2SiO4 + L = Ca3Si2O7) and follows within the temperature
interval 1400–1317 °C until the peritectic point K when larnite reacts
with liquid K to produce rankinite and gehlenite (Ca2SiO4 + L =
Ca3Si2O7 + Ca2Al2SiO7). Any larnite formed is predicted by the theory
to disappear completely at the point K, but it survives as mineral inclu-
sions in melilite crystals. Cooling continues with coprecipitation of
rankinite and gehlenite until they are joined by pseudowollastonite
at the eutectic N. In natural rocks, melilite changes its composition
while crystallizing from gehlenite to ferrigehlenite. Further cooling re-
sults in crystallization of sporadic crystals of late wollastonite. Subse-
quent temperature drop of residual liquid rich in Fe 3 +, Ti, and F is
rather abrupt, as one may infer from the habits of later quenching
minerals, namely Ti-rich andradite and cuspidine.
The experimental results fitted quite well the temperatures de-
rived from the CaO–SiO2–Al2O3 diagram through the real crystalliza-
tion occurred not exactly at the predicted temperatures. We failed
to melt paralava sample 12D in the VTP-06 furnace at T = 1500 °C
which turned out to be below its liquidus. The melt inclusions in ran-
kinite heated to T = 1320 °C remained not completely homogenized
(Sokol et al., 2010).
Thus, the melts that originally were more basic (Ca/Si ~1.3) under-
went a more complicated crystallization path on cooling which led
eventually to extensive crystallization of pseudowollastonite. The for-
mation of pseudowollastonite with trisilicate rings [Si3O9] in its struc-
ture instead of wollastonite chains may be further maintained, besides
the heating much above the Pwo → Wo phase boundary, by depoly-
merization of silicate liquid with a high Ca/Si ratio.
Unlike the CaO–Al2O3–SiO2 system, there is no eutectic crystalliza-
tion of pseudowollastonite in the systems CaO–MgO–SiO2 and CaO–
FeO–SiO2 where the low-temperature CaSiO3ss → Pwo reversion

Fig. 8. The system CaO–Al2O3–SiO2 (wt.%) at an ambient pressure (after Osborn and
Muan, 1960) showing crystallization paths of paralava samples 21 (a) and 12D (b).
Squares show bulk compositions of samples. The compositions of the crystallizing
melts change according to the dash lines. Temperature in degrees Celsius. See text
for explanation.

the Pwo-Gh cotectic at Ttheor b 1310 °C. Crystallization followed by copre-

cipitation of CaSiO3 and gehlenite-rich melilite (Ttheor. =1310–1265 °C)
as we deduced from both diagram and textural evidence. The presence
of sporadic late wollastonite laths prompts residual liquid to exist at a
temperature below the Psw → Wo transition (Ttheor. =1125 °C). The
paralava textures indicate that Ti-rich andradite appears shortly before
the melt crystallization endpoint and then forms typical eutectic inter-
growths with nagelschmidtite (so-called “tubular eutectic”). At that
point, the residual liquid departs from the CaO–SiO2–Al2O3 composition
and cannot be shown in the diagram. The Fe3 +, Ti, P, Na, K, and F concen-
trations in the residual liquid become sufficient for Ti-rich andradite,
nagelschmidtite, and cuspidine to crystallize. Thus, the diagram for the
system CaO–SiO2–Al2O3, along with petrographic evidence and X-ray
characteristics of three coexisted CaSiO3 modifications, allows the fol-
lowing inference. Three CaSiO3 modifications crystallized within the
pseudowollastonite stability field from a liquid at least 400 °C hotter
than the Pwo→Wo phase boundary with its bulk chemistry at about
CaSiO3 stoichiometry. The growth of dominant parawollastonite (2M),
with lamellae of subordinated wollastonite (1T), was metastable and
was accompanied by crystallization of minor amounts of stable
pseudowollastonite.
Representative pseudowollastonite-bearing paralava sample 12D is Fig. 9. The Ca-rich fragment of the phase diagram of the binary CaSiO3–FeSiO3 system
highly enriched in CaO (48 wt.%) and contains much less SiO2 (after Deer et al., 1997).
88 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90

temperature rises highly for the existence of the solid solutions of diop-
side or/and hedenbergite (Figs. 9, 10). For the same reason, the bound-
ary between the phase volumes of pseudowollastonite and low-
temperature CaSiO3ss is not a line of constant temperature (Grapes,
2011; Morey, 1963).
Within the binary system CaSiO3–CaFeSi2O6, the reversion tempera-
ture of low-temperature CaSiO3ss (Woss or bustamite) to pseudowollas-
tonite is 135 °C higher (T= 1285 °C) (Fig. 9). When melts containing
0–43 wt.% FeSiO3 cool down, the liquid begins to crystallize at
1548–1285 °C with precipitation of pure Pwo and becomes completely
crystalline at 1285 °C. Melts of narrow compositions between CaSiO3
and the point B (9 wt.% FeSiO3) consist of Pwo and Woss at T =
1285 °C. On further cooling, the composition of the wollastonite solid
solution changes along the curve BA at the expense of Pwo which even-
tually disappears at 1160 °C.
Cooling of melts with 9–43 wt.% FeSiO3 first leads to crystallization
of CaSiO3ss (or bustamite) at 1285 °C at the expense of pseudowollas-
tonite (α-CaSiO3 + L1 → low-temperature CaSiO3ss + L2). Once Pwo
has entirely disappeared, further cooling results in low-temperature
CaSiO3ss crystallization and simultaneous changes in composition of
both liquid and solid phases. That was most likely the scenario followed
by Pwo and Woss that formed and remained preserved in the igneous
rocks of Colle Fabbri.
Crystallization and subsequent disappearance of pseudowollasto-
nite within the system CaO–MgO–SiO2 are generally similar to the
cases above (Fig. 10a). The reversion temperature of Mg-Wo → Pwo

Fig. 10. The crystallization field of pseudowollastonite in systems CaSiO3–CaMgSi2O6 (a) (after Jung et al., 2005) and CaO–Al2O3–SiO2–MgO at 5 wt.% and 10 wt.% MgO (b) (after
Grapes, 2011). See text for explanation.
 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90
rises from 1125 °C to 1370 °C, so that Mg–Wo has a field at the liqui-
dus surface of the ternary system CaO–MgO–SiO2 (Deer et al., 1997;
Grapes, 2011; Jung et al., 2005; Morey, 1963) (Fig. 10b). If the melt
contains more than 10 mol% MgSiO3, at 1370 °C (horizontal C–D),
pseudowollastonite disappears and Mg-Wo forms (α-CaSiO3 + L1 →
Mg-Wo+ L2). Further cooling produces a region of Mg-Wo solid
solutions.
Thus, the peritectic temperature in the discussed systems with
clinopyroxenes is the minimum at which pseudowollastonite can co-
exist in equilibrium with liquids. Morey (1963) estimated it at 1272 °C
(for ferrous compositions) while Deer et al. (1997) gave a slightly higher
value of 1285 °C. It is only within narrow composition fields between
CaSiO3 and the point with ~10% (Fe,Mg)SiO3 that the two-phase domain
of Woss-Pwo coexistence can reach, pinching out, T =1125 °C. As these
rocks cool down slowly, pseudowollastonite cannot survive being trans-
formed entirely into low-temperature CaSiO3 solid solutions. Its preser-
vation as a relict phase becomes possible only on rock (melt) quenching.
9.3. Application to natural assemblages
The evidence from the comparison with the experimental systems
(CAS; CMS; CFS; CMAS + FeO) and the limited occurrence of natural
pseudowollastonite-bearing assemblages indicate which conditions
are required for this mineral to form in nature. It most likely can be
expected to exist in high-temperature melt rocks with a SiO2:(Mg,
Fe)O ratio lower than in metasilicate and with high Ca. The crystalli-
zation domain of pseudowollastonite is the largest in the system
CaO–Al2O3–SiO2 (CAS), where the lower bound of its appearance at
ambient pressure corresponds to 1125 °C. In liquids with more complex
compositions, its crystallization temperature exceeds 1208° ± 3 °C for
CAS + Fe2O3 (Grapes, 2011) and T > 1235 °C for CMAS + FeO (melting
point of Pwo+ CPx + Mel + An) (Morey, 1963). Pseudowollastonite
can survive only on quenching of these fully or partially crystalline
rocks, which is possible when they cool down near the surface.
Indeed, all pseudowollastonite-bearing igneous rocks and paralavas
found so far differ in considerable CaO enrichment and are larnite-
normative. They have abnormal melting temperatures reaching
1330 °C and 1500 °C for paralavas (Darreh Harrachi and Nabi Musa lo-
calities, correspondingly) and T > 1308 °C for Colle Fabbri melilitites
(Grapes, 2011). Liquids in all cases crystallized immediately near the
surface and then quenched rapidly, judging by the presence of glass
and various quench textures. Pseudowollastonite, always correspond-
ing to pure CaSiO3, is associated with melilites and with diverse ferric
(Fe3 +) minerals. The redox conditions of melt cooling likewise may
have played an important role in its crystallization and subsequent
preservation. In a moderately reduced environment, increase in ferrous
iron (Fe2 +) inevitably leads to the formation of low-temperature
CaSiO3ss at the expense of pseudowollastonite. The melts we discussed,
which cooled near the surface, were dominated by ferric iron (Fe3 +). In
rocks this iron is mostly bound in melilite solid solutions (mainly ferri-
gehlenite Ca2Fe3 +2SiO7) and Ti-rich andradites (both in the Mottled
Zone paralavas and Colle Fabbri melilitolites), as well as in aegirine–
augite and Al-, Ti-, and Fe3 +-rich clinopyroxene (Darreh Harrachi para-
lavas and Colle Fabbri melilitolites, correspondingly).
At the same time, our experience of studying the Nabi Musa parala-
vas shows that polytype and polymorphic modifications of CaSiO3 com-
pete even at the optimal crystallization conditions. Wollastonite and
parawollastonite can crystallize in the stability field of pseudowollasto-
nite (sample 21). The preferential formation of a polytype is mainly
governed by kinetic factors while crystallization of polymorphs is
under either thermodynamic or kinetic control. Many research studies
done in this regard have revealed that supersaturation by oneself as
well as the rate of supersaturation generation and the tendency of the
formation of the less stable polymorph is positively correlated. Kinetic
effects are dominant when the rate of supersaturation generation is
high, thereby producing the metastable polymorphs; on the contrary,
89
more stable polymorphs are formed when the rate of supersaturation
generation is low and the thermodynamic effects are prevailing
(Barrett et al., 2010; Peters, 2011; Putnis, 1992). In the case of study
the melt corresponding to the paralava sample 21 was very close to
CaSiO3 stoichiometry and hence was more saturated as compared
with the melt composition 12 (Table 1).
There is some (rather low) probability that pseudowollastonite
may appear as a product of solid-phase reactions, including in horn-
fels. The minimum temperatures and the largest stability field (be-
tween 1135° ± 10° and 1208° ± 3 °C) for pseudowollastonite are in
the system CMAS + Fe2O3 (Grapes, 2011). Pseudowollastonite-
bearing hornfels were discovered only once, in the Hatrurim complex
of the Mottled Zone (Sokol et al., 2008). Inasmuch as these tempera-
tures are common to combustion metamorphism caused by ignition
of hydrocarbons, time was likely the crucial factor. Both heating of
the protolith and cooling of hornfels require orders of magnitude longer
time than melting and quenching of CM melts. That is why Pwo → Wo
reversion may be possible in the case of solid-phase reactions but no-
body has ever observed it in natural systems.
Acknowledgments
We wish to thank Prof. Rodney Grapes (University of Wellington,
New Zealand) for thoughtful discussions which have shaped up our
idea of pyrometamorphic events. We are grateful to Prof. Marco Scam-
belluri, a “Lithos” chief editor, the reviewer Prof. Giancarlo Capitani
(University of Milano-Bicocca, Italy) and an anonymous referee whose
thoughtful criticism inspired more insights and diversification in our
analysis of CaSiO3 polymorphism in nature. More thanks go to Dr.
Yevgeny Vapnik (Ben-Gurion University of the Negev, Beer-Sheva,
Israel) and Dr. Victor Sharygin (Sobolev Institute of Geology and
Mineralogy, Novosibirsk, Russia) and Prof. F. Scordari (University of
Bari, Italy) for information and valuable discussions. We are grateful
to Dr. E. Nigmatulina, (Sobolev Institute of Geology and Mineralogy, No-
vosibirsk, Russia) for the analytical work. Thanks are extended to
Tatyana Perepelova, our translator, for improving and clarifying the
English text. The study was supported by grant 09-05-00285 from
the Russian Foundation for Basic Research, grant MK-6750.2010.5
from the President of the Russian Federation and grant ONZ-8 from pre-
sidium of Division of Earth Sciences of Russian Academy of Sciences.
References
Barrett, M., McNamara, M., Hao, H.X., Barrett, P., Glennon, B., 2010. Supersaturation
tracking for the development, optimization and control of crystallization process-
es. Chemical Engineering Research and Design 88, 1108–1119.
Basi, M.A., Jassim, S.Z., 1974. Baked and fused Miocene sediments from Injana area,
Hemrin South, Iraq. Journal of the Geological Society of Iraq 7, 1–14.
Bentor, Y.K., Gross, S., Heller, L., 1963. Some unusual minerals from the “Mottled Zone”
complex, Israel. American Mineralogist 48, 924–930.
Bredig, M.A., 1943. Phase relations in the system calcium orthosilicate–orthophosphate.
American Mineralogist 28, 594–601.
Burg, A., Kolodny, Ye, Lyakhovsky, V., 1999. Hatrurim-2000: the “Mottled Zone” revisited,
forty years later. Israel Journal of Earth Sciences 48, 209–223.
Cisowski, S.M., Fuller, M., 1987. The generation of magnetic anomalies by combustion
metamorphism of sedimentary rocks, and its significance to hydrocarbon explora-
tion. Geological Society of America Bulletin 99, 21–29.
Deer, W.A., Howie, R.A., Zussman, J., 1997. Rock-forming minerals, second ed. Single-
chain Silicates, Vol. 2. Geological Society Publishing House, London.
Essene, E., 1974. High-pressure transformations in CaSiO3. Contributions to Mineralogy
and Petrology 45, 247–250.
Foit, F.F., Hooper, R.L., Rosenberg, P.E., 1987. Unusual pyroxene, melilite, and iron oxide
mineral assemblage in coal-fore buchite from Buffalo, Wyoming. American Miner-
alogist 72, 137–147.
Grapes, R., 2011. Pyrometamorphism, second ed. Springer, Berlin.
Gross, S., 1977. The mineralogy of the Hatrurim formation, Israel. Geological Survey of
Israel Bulletin 70, 1–80.
Henmi, C., Kusachi, I., Kawahara, A., Henmi, K., 1978. 7 T wollastonite from Fuka, Okayama
Prefecture. Mineralogical Journal 9, 169–181.
Henmi, C., Kawahara, A., Henmi, K., Kusachi, I., Takeuchi, Y., 1983. The 3 T, 4 T and 5 T
polytypes of wollastonite from Kushiro, Hiroshima Prefecture. Japan. American
Mineralogist 68, 15–163.
90 Y.V. Seryotkin et al. / Lithos 134-135 (2012) 75–90
Hutchison, J.L., McLaren, A.C., 1976. Two-dimensional lattice images of stacking disorder
in wollastonite. Contribution to Mineralogy and Petrology 55, 303–309.
Ingrin, J., 1993. TEM imaging of polytypism in pseudowollastonite. Physics and Chemistry
of Minerals 20, 56–62.
Jung, I.H., Decterov, S.A., Pelton, A.D., 2005. Critical thermodynamic evaluation and optimi-
zation of the CaO–MgO–SiO2 system. Journal of the European Ceramic Society 25,
313–333.
Khesin, B., Vapnik, Ye, Itkis, S., 2010. Geophysical evidence of deep hydrocarbon flow in
Mottled Zone areas, Dead Sea Transform zone. Geophysics 75, 91–101.
Kushiro, I., 1964. Wollastonite–pseudowollastonite inversion. Carnegie Institution of
Washington Year Book 63, 83–84.
Lindsley, D.H., Brown, G.M., Muir, I.D., 1969. Conditions of the ferrowollastonite–
ferrohedenbergite inversion in the Skaergaard intrusion, East Greenland. In:
Parike, J.J. (Ed.), Pyroxenes and Amphiboles: Crystal Chemistry and Phase Petrology:
Mineralogical Society of America, Special Paper, No 2, pp. 193–201.
Lore, J., Eichhubl, P., Aydin, A., 2002. Alteration and fracturing of siliceous mudstone
during in situ combustion, Orcutt field, California. Journal of Petroleum Science
and Engineering 36, 169–182.
Longhi, J., 1987. Liquidus equilibria and solid solution in the system CaAl2Si2O8–
Mg2SiO4–CaSiO3–SiO2 at low pressure. American Journal of Science 287, 265–331.
Matthews, A., Gross, S., 1980. Petrologic evolution of the “Mottled Zone” (Hatrurim)
metamorphic complex of Israel. Israel Journal of Earth Sciences 40, 107–124.
Mazzucato, E., Gualtieri, A.F., 2000. Wollastonite polytypes in the CaO–SiO2 system.
Physics and Chemistry of Minerals 27, 565–574.
McLintock, W.F.P., 1932. On the metamorphism produced by the combustion of hydro-
carbons in the Tertiary sediments of south-west Persia. Mineralogical Magazine 29,
93–106.
Melluso, L., Conticelli, S., D'Antonio, M., Mirco, N.P., Saccani, E., 2003. Petrology and
mineralogy of wollastonite- and melilite-bearing paralavas from the Central Apennines,
Italy. American Mineralogist 88, 1287–1299.
Morey, G., 1963. Phase equilibrium relations of the common rock-forming oxides except
water, In: Fleischer, M. (Ed.), Data of Geochemistry, 6th ed. United States Government
Printing Office, Washington, pp. 1–180.
Ohashi, Y., 1984. Polysynthetically-twinned structures of enstatite and wollastonite.
Physics and Chemistry of Minerals 10, 217–229.
Osborn, E.F., Muan, A., 1960. Phase equilibrium diagrams of oxide systems, plate 1. The
System CaO–Al2O3–SiO2. American Ceramic Society and the Edward Orton, Ir., Ceramic
Foundation, Columbus, Ohio.
Osborn, F.F., Schairer, J.F., 1941. The ternary system pseudowollastonite–akermanite–
gehlenite. American Journal of Science 239, 715–763.
Peters, B., 2011. Supersaturation rates and schedules: nucleation kinetics from isothermal
metastable zone widths. Journal of Crystal Growth 317, 79–83.
Putnis, A., 1992. Introduction to Mineral Sciences. Cambridge University Press,
Cambridge.
Reverdatto, V.V., 1973. The Facies of Contact Metamorphism. Australian National University,
Canberra, ACT.
Richet, P., Mysen, B.O., Ingrin, J., 1998. High-temperature X-ray diffraction and Raman
spectroscopy of diopside and pseudowollastonite. Physics and Chemistry of Minerals
25, 401–414.
Rietmeijer, F.J.M., 1999. Metastable non-stoichiometric diopside and Mg-wollastonite:
an occurrence in an interplanetary dust particle. American Mineralogist 84,
1883–1894.
Rivenet, M., Cousin, O., Boivin, J.C., Abraham, F., Ruchaud, N., Hubert, P., 2000. A study of
the Na2O–CaO–P2O5–SiO2 system with respect to the behaviour of phosphate
bonded basic refractories at high temperature. Journal of the European Ceramic Society
20, 1169–1178.
Scott, P.W., Critchley, S.R., Wilkinson, F.C.F., 1986. The chemistry and mineralogy of some
granulated and palletized blast furnace slags. Mineralogical Magazine 50, 141–147.
Sharygin, V.V., Sokol, E.V., Vapnik, Ye, 2008. Minerals of the pseudobinary perovskite–
brownmillerite series from combustion metamorphic larnite rocks of the Hatrurim
Formation (Israel). Russian Geology and Geophysics 49, 709–726.
Sheldrick, G.M., 2008. A short history of SHELX. Acta Crystallographica A64, 112–122.
Shinno, I., 1970. A consideration on the crystallization process of diopside. Journal of
Japanese Association of Mineralogy, Petrology, and Economic Geology 63, 146–159.
Sokol, E.V., Novikov, I.S., Vapnik, Ye, Sharygin, V.V., 2007. Gas fire from mud volcanoes
as a trigger for the appearance of high temperature pyrometamorphic rocks of the
Hatrurim Formation (Dead Sea area). Doklady Earth Sciences 413, 474–480.
Sokol, E.V., Novikov, I.S., Zateeva, S.N., Sharygin, V.V., Vapnik, Ye, 2008. Pyrometamorphic
rocks of the spurrite–merwinite facies as indicators of discharge zones of hydrocar-
bons (the Hatrurim Formation, Israel). Doklady Earth Sciences 420, 608–614.
Sokol, E., Novikov, I., Zateeva, S., Vapnik, Ye, Shagam, R., Kozmenko, O., 2010. Combustion
metamorphism in Nabi Musa dome: new implications for a mud volcanic origin of the
Mottled Zone, Dead Sea area. Basin Research 22, 414–438.
Stoppa, F., Sharygin, V.V., 2009. Melilitolite intrusion and pelite digestion by high tem-
perature kamafugitic magma at Colle Fabbri, Spoleto, Italy. Lithos 112, 306–320.
Swamy, V., Dubrovinsky, L.S., 1997. Thermodynamic data for the phases in the CaSiO3
system. Geochimica et Cosmochimica Acta 61, 1181–1191.
Techer, I., Khoury, H.N., Salameh, E., Rassineux, F., Claude, C., Clauer, N., Pagel, M., Lancelot,
J., Hamelin, B., Jacquot, E., 2006. Propagation of high-alkaline fluids in an argillaceous
formation: case study of the Khushaym Matruk natural analogue (Central Jordan).
Journal of Geochemical Exploration 90, 53–67.
Trojer, F.J., 1968. The crystal structure of parawollastonite. Zeitschrift für Kristallographie
127, 291–308.
Vapnik, Y., Sharygin, V.V., Sokol, E.V., Shagam, R., 2007. Paralavas in a combustion
metamorphic complex: Hatrurim Basin, Israel. In: Stracher, G.B. (Ed.), Geology of
Coal Fires: Case Studies from Around the World: Geological Society of America Re-
views in Engineering Geology, v. XVIII, pp. 133–153.
Yamanaka, T., Mori, H., 1981. The structure and polytypes of α-CaSiO3 (pseudowollastonite).
Acta Crystallographica B37, 1010–1017.
Yang, H., Prewitt, C.T., 1999a. On the crystal structure of pseudowollastonite (CaSiO3).
Journal of the European Ceramic Society 84, 929–932.
Yang, H., Prewitt, C.T., 1999b. Crystal structure and compressibility of a two-layer polytype
of pseudowollastonite (CaSiO3). American Mineralogist 84, 1902–1905.
Whitney, D.L., Evans, B.W., 2010. Abbreviations for names of rock-forming minerals.
American Mineralogist 95, 185–187.
Žáček, V., Skála, R., Chlupáčová, M., Dvořák, Z., 2005. Ca–Fe3 +-rich Si-undersaturated
buchite from Zelenky, North Bohemian Brown Coal Basin, Czech Republic. European
Journal of Mineralogy 17, 623–633.