JOURNAL OF PETROLOGY VOLUME 45 NUMBER 7
1093/petrology/egh022
Towards a Better Understanding of the
Fibrolite Problem: the Effect of Reaction
Overstepping and Surface Energy Anisotropy
R. SASSI1*, C. MAZZOLI1,2, R. SPIESS1,2 AND T. CESTER1
1
DEPARTMENT OF MINERALOGY AND PETROLOGY, UNIVERSITY OF PADOVA, C.SO GARIBALDI 37, 35137 PADOVA,
ITALY
2
IST. GEOSCIENZE GEORISORSE, CNR, C.SO GARIBALDI 37, 35137 PADOVA, ITALY
RECEIVED DECEMBER 1, 2002; ACCEPTED FEBRUARY 2, 2004
Trachytes from the Euganean Hills District (Italy) contain meta-
pelitic xenoliths that have been pyrometamorphosed during incor-
poration in the melt. In xenoliths containing sillimanite crystallized
during a previous regional HT/LP metamorphism, fibrolite system-
atically nucleates at the grain boundaries of sillimanite prisms and
within plagioclase crystals. Ternary feldspar thermometry shows that
plagioclase in contact with sillimanite plots along the 750
C solvus
that reflects near-equilibrium conditions of regional metamorphism.
Plagioclase containing fibrolite plots closer towards the 950
C solvus,
reflecting the tendency of plagioclase to re-equilibrate at high temp-
erature during pyrometamorphism by a fibrolite-forming reaction:
K -feldspar ð1Þ þ plagioclase ð1Þ
! K -feldspar ð2Þ þ plagioclase ð2Þ þ fibrolite:
In sillimanite-free xenoliths, fibrolite did not form during pyro-
metamorphism, because these xenoliths do not contain plagioclase.
In these xenoliths, andalusite prisms are replaced by oriented fibrous
corundum needles and K-feldspar. The petrographic evidence suggests
that when reaction rate is high as a result of reaction temperature
overstepping, sillimanite grows as fibrolite because the surface energy
of {110} faces is low and their growth rate is rapid. The same
explanation may hold also for the growth of acicular corundum
pseudomorphing andalusite prisms in sillimanite-free xenoliths.
KEY WORDS: andalusite breakdown; fibrolite; pelitic xenoliths; reaction
overstepping; sillimanite
INTRODUCTION
Fibrolite is the fine-grained, acicular high-temperature
variety of Al2SiO5 and almost invariably forms in
*Corresponding author. Telephone: þ39-049-8272019. Fax: þ39-049-
8272010. E-mail: raffaele.sassi@unipd.it.
PAGES 1467–1479 2004 DOI: 10.
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metapelites when the sillimanite stability field is
approached, either from the kyanite or from the andalu-
site field. There is a continuum between acicular fibrolite
and prismatic sillimanite, so that a clear-cut distinction
between them cannot be made on the basis of grain
size or habit. However, if potential contribution of
grain boundary energy to total free energy is considered
(Holdaway, 1971; Kerrick, 1990; Hemingway et al.,
1991), then crystals with a diameter of less than 2 mm
should be regarded as fibrolite rather than sillimanite
(Kerrick, 1990; Pattison, 1992). Herein we adhere to
this distinction. In this definition, it is implicit that fibro-
lite has a higher molar free energy than coarse-grained
sillimanite. Thus, the common observation that fibrolite
appears earlier than sillimanite conflicts with equilibrium
thermodynamics; consequently the fibrolite ‘problem’
has been debated over recent decades.
Metastable formation of fibrolite is a possible explana-
tion. Hints for metastability come from garnet–biotite
geothermometry (Fleming, 1973; Kerrick, 1987), which
show that calculated KD values indicative for fibrolite
formation occur outside the sillimanite stability field.
Epitaxial growth lowering the energy of nucleation for
fibrolite is an alternative explanation that is suggested
by the widespread observation that fibrolite frequently
shows a regular, triangular arrangement pattern within
basal sections of biotite (Chinner, 1961; Yardley, 1977).
Kerrick (1987) has suggested that fibrolite may inherit the
trigonal arrangement of Si and Al chains in the tetra-
hedral layers of the biotite structure, so that fibrolite
nucleation is favoured over andalusite or kyanite nuclea-
tion. Therefore, when dehydration reactions affecting
Journal of Petrology 45(7) # Oxford University Press 2004; all rights
reserved.
 JOURNAL OF PETROLOGY VOLUME 45 NUMBER 7 JULY 2004

(a) (b)
ene
L ine N 50
45
v
- Pio 40
ana Schio

Brenta
r 45
Ma Marostica Hills 50 (a) 35
55 20
25 30
30 35
ITALY
Lessini Vicenza 45
Mts.

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25

Sc
20

hi
o
Vi
ce
Venetian Volcanic Province
Berici

nz
a
Hills

Li
Mesozoic and Tertiary

ne
sedimentary rocks
Ca

Ad
ige
ste

Alluvial deposits
lve
ro
Lin

Main faults
e

Euganean Hills
0 5 10 km

Fig. 1. (a) Schematic map of Venetian Volcanic Province, modified after Milani et al. (1999). (b) Moho isobaths (in km) in Northern Italy, from
Giese & Buness (1992).

biotite are involved in forming the Al2SiO5 polymorph
reactant at high temperature, a potentially lower nuclea-
tion energy for fibrolite may explain its crystallization
instead of sillimanite growth.
However, fibrolite is also found to occur across ex-
tremely sharp kyanite–sillimanite isograds (Grambling,
1981; Grambling & Williams, 1985) where there is micro-
structural evidence of kyanite being replaced by fibro-
lite. In this case, we are dealing with a real paramorphic
transformation.
The above examples clearly show that fibrolite system-
atically forms before sillimanite. Therefore, the contribu-
tion of the surface energy of fibrolite to the total free
energy must have no influence on the earlier stability of
fibrolite vs sillimanite. At the same time, it is not reason-
able to claim that the consistent appearance of fibrolite
before sillimanite is explained in every case by metastable
or epitaxial growth. It is, therefore, more likely that
fibrolite formation is driven by kinetic factors and to
understand these we need to focus on examples where
such factors can be constrained. This is possible only
where fibrolite formation can be linked to specific
changes of the physical parameters controlling the
metamorphism. Such an opportunity is given by meta-
pelites that have undergone pyrometamorphism when
they were included as xenoliths in trachytic magma of
the Euganean Hills (NE Italy). The results of our
investigations indicate a mechanism of fibrolite formation
that implies an initially accelerated growth rate as a result
of reaction overstepping of a mineral that is characterized
by a strongly anisotropic surface energy.
GEOLOGICAL SETTING
The Euganean Hills District belongs to the wider
Venetian Volcanic Province (Fig. 1a), which covers an
area of 2000 km2 in NE Italy. The most representative
rock types of the Euganean Hills District are Late Eocene
to Oligocene trachytes, rhyolites, latites and basalts (Borsi
et al., 1969). Geochemical (De Vecchi & Sedea, 1974;
De Vecchi et al., 1976; and references quoted therein) and
geophysical data (Giese & Buness, 1992) are consistent
with an extensional geodynamic context (Fig. 1b). This
agrees with the widespread occurrence of numerous
extensional tectonic faults with NNE–SSW and NW–
SE direction (Fig. 1a) related to the volcanic activity
(Piccoli et al., 1981; Barbieri et al., 1991; Castellarin et al.,
1992; Zampieri, 1995).
Geophysical data indicate the Moho at 30 km depth
underneath the Euganean Hills District, giving a lower
constraint to the possible source depth for the xenoliths.
On the other hand, crystalline basement has been found
at 47 km in boreholes under the Venice lagoon (Meli &
Sassi, 2003), giving an upper constraint.

1468
 SASSI et al. ON THE FIBROLITE PROBLEM
THE XENOLITHS IN TRACHYTES OF
THE EUGANEAN HILLS AND THEIR
PETROGRAPHIC FEATURES
Oligocene trachytes from the Euganean Hills include
various types of regionally metamorphosed gneissic xeno-
liths. Currently, age constraints for the regional high-T–
low-P metamorphism are not available, but this could
be related to magma production in the Euganean Hills
District.
Some of the xenoliths have a pelitic composition, and
preserve replacement microstructures that indicate a
complex metamorphic history involving Al2SiO5 phase
transformations. In addition, they also preserve micro-
structural and petrological evidence that may help to
understand one of the long-lasting problems in meta-
morphic petrology: what drives fibrolite formation?
The xenoliths considered in this paper are slightly
elongated and of a few centimetres in length. Two main
types are recognized: type (i), sillimanite-bearing andalu-
site gneiss, consisting of sillimanite, fibrolite, andalusite,
corundum, alkali feldspars, plagioclase, biotite, green spi-
nel, magnetite and ilmenite (samples MM182, MM188
and MM189); type (ii), sillimanite-free andalusite–
cordierite gneiss, consisting of andalusite, corundum,
alkali feldspars, biotite, green spinel, magnetite, ilmenite
and cordierite (samples MM29, CZ12 and CZ16).
The gneissic structure of the xenoliths is mainly de-
fined by the orientation of Al2SiO5 crystals. Grain size is
highly variable, because of the presence of large an-
dalusite, sillimanite and alkali feldspar (up to 15 mm)
and small grains of green spinel, magnetite and ilmenite
(<50 mm). In some xenoliths both recrystallized and
glassy melt pools occur. In detail, several microstruc-
tural domains are present within each of the two main
xenolith types.
Type (i)—sillimanite-bearing andalusite
gneiss
(1) The occurrence of large, ‘isolated’, inclusion-free
porphyroblasts of andalusite is a distinctive microstruc-
tural feature of this rock type. The porphyroblasts display
rounded edges and are often embayed (Fig. 2a). They are
always located within alkali feldspar-rich, plagioclase-
bearing, biotite-, spinel- and opaque-free domains.
(2) Large prismatic sillimanite crystals (up to 3 mm
in size), defining the main foliation of the rock,
occur together with K-feldspar and plagioclase, and are
surrounded by biotite-free, magnetite-, ilmenite- and
spinel-rich coronas (Fig. 2b). Crystal boundaries of the
sillimanite prisms are invariably irregular, indicating that
a sillimanite-consuming reaction has occurred.
(3) Fibrolite systematically nucleates at the grain
boundaries or along cleavage planes of sillimanite prisms
1469
(Fig. 2b and c), within plagioclase (Fig. 2d), and extends
into the surrounding matrix. Fibrolite is never associated
with andalusite.
(4) Small corundum idioblasts occur within ‘isolated’
andalusite and sillimanite prisms (Fig. 2e) and, more
rarely, in the matrix.
(5) Biotite-rich domains are sillimanite-free, and are
always isolated from sillimanite prisms. Biotite is trans-
formed to varying extents to an aggregate of K-feldspar,
green spinel, and ilmenite (Fig. 2f ).
(6) Large magnetite crystals show exsolution lamellae of
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ilmenite and spinel.
Type (ii)—sillimanite-free
andalusite–cordierite gneiss
(1) This rock type is characterized by bands of oriented
andalusite idioblasts alternating with bands of K-feldspar
and cordierite. Both bands are characterized by inclu-
sion trails of spinel and ilmenite that define a former
foliation. The inclusion trails are more common within
the K-feldspar–cordierite bands, suggesting that they
have replaced former biotite-rich bands, whereas the
andalusite-rich bands represent former muscovite-rich
bands (Fig. 3a).
(2) In some cases, andalusite appears to be in equili-
brium with cordierite and K-feldspar as shown by stumpy
granular boundaries (MM29); in other cases it is clearly
replaced by K-feldspar (CZ12), indicating that an
andalusite-consuming reaction boundary has been
crossed.
(3) Locally, relics of biotite occur, although biotite is
largely transformed to an aggregate of K-feldspar, green
spinel, magnetite and ilmenite.
(4) Small corundum idioblasts are included within
K-feldspar (CZ12). Their orientation is parallel to that
of spinel and ilmenite inclusion trails, suggesting a forma-
tion related to the breakdown of a former foliation-
forming phase such as muscovite. Locally, corundum
porphyroblasts occur that include inclusion trails of spinel
(Fig. 3b).
(5) Corundum also occurs as large blue idioblasts, and
is clearly growing at the expense of andalusite (Fig. 3c).
(6) In some cases (CZ16) andalusite porphyroblasts are
extensively replaced by a fine- to very fine-grained aggre-
gate of acicular corundum in a matrix of K-feldspar
(Fig. 3d–f ).
MINERAL CHEMISTRY
Microprobe analyses were carried out using a Cameca
Camebax electron microprobe (IGG-CNR–Department
of Mineralogy and Petrology, University of Padova).
Operating conditions were: electron beam current
10 nA; accelerating voltage 15 kV; acquisition time 10 s
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Fig. 2. Microstructural features of sillimanite-bearing andalusite gneisses. (a) Embayed andalusite (And) porphyroblast surrounded by K-feldspar
(Kfs) and plagioclase (Pl) crystallized from melt. (b) Fibrolite (Fib) nucleating at the grain boundaries of sillimanite prisms; no fibrolite nucleates on
andalusite. (c) Electron forescatter image (EFI) of fibrolite nucleating at the grain boundaries of sillimanite, invading the surrounding matrix.
(d) Fibrolite nucleating within plagioclase close to K-feldspar (section cut perpendicular to the c-axes of fibrolite). (e) Corundum (Crn) idioblasts
growing at the expense of sillimanite prism. (f ) Biotite (Bt) reacting to K-feldspar þ spinel (Spl) þ ilmenite (Ilm). Abbreviations after Kretz (1983).

for each element and 5 s on background; beam radius Ilmenite

1 mm. Natural and synthetic standards were used, and the
PAP correction procedure was followed. Analytical mea-
surements are affected by a relative uncertainty of 1% for
the major elements (>5 wt %) and 4% for the minor
elements (<5 wt %). Representative analyses of the main
mineral phases are listed in Table 1.
Figure 4 shows the composition of ilmenite (triangles) in
the system TiO2–FeO–Fe2O3. With respect to the ideal
composition, ilmenites from microdomains containing
green spinel and biotite (open triangles, sample
MM189) have moderate amounts of Fe3þ (013–015
a.p.f.u., normalized to three oxygens), whereas ilmenites

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 SASSI et al. ON THE FIBROLITE PROBLEM

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Fig. 3. Microstructural features of sillimanite-free andalusite–cordierite gneisses. (a) Bands of isoriented andalusite (And) idioblasts alternating
with K-feldspar (Kfs) and cordierite (Crd) bands; spinel and ilmenite inclusions trace a regional metamorphic foliation. (b) Corundum (Crn)
porphyroblasts with spinel and ilmenite inclusion trails. (c) Corundum idioblasts after andalusite. (d–f ) Andalusite porphyroblasts extensively
replaced by acicular corundum and K-feldspar; plane-polarized light (d), electron backscattered (e) and electron forescattered (f ) images.
Abbreviations after Kretz (1983).

from K-feldspar-rich domains (filled triangles, sample Magnetite

CZ12) have nearly ideal stoichiometry (Fe3þ ¼ 0015–
0023 a.p.f.u.). Ilmenite also occurs as exsolved lamellae
within magnetite idioblasts (Fig. 5), but the extremely
small size of the lamellae precludes electron microprobe
analysis.
Magnetite forms large idioblasts only within sample
MM189. Figure 4 shows their composition (open
squares). The data points fall within the titanomagnetite
field, along the ulv€ospinel–magnetite tie-line, but close to
the ideal magnetite composition. The magnetites have a

1471
 Table 1: Representative mineral compositions from different microstructural sites (sample MM189)

Ilm Mag Spl Pl Pl Kfs Crn And And Sil Fibr Bt Bt

Sample: MM189 MM189 MM189 MM189 MM189 MM189 MM189 MM189 MM189 MM189 MM189 MM189 MM189
near Bt on Bt around Sil around Fib around Fib core core rim

SiO2 0.04 0.00 0.04 57.63 60.18 64.69 0.04 36.54 35.98 36.18 36.63 SiO2 36.43 35.98
TiO2 43.05 2.12 0.31 0.00 0.01 0.08 0.04 0.17 0.05 0.01 0.02 TiO2 5.34 7.89
Al2O3 0.28 4.75 53.51 26.26 25.07 19.73 99.06 60.59 61.05 62.10 61.91 Al2O3 17.26 16.48
Cr2O3 0.00 0.09 0.18 0.00 0.00 0.00 0.07 0.03 0.05 0.08 0.02 Cr2O3 0.03 0.05
FeO 51.53 31.63 32.10 0.20 0.08 0.37 1.10 FeO 11.72 11.74
Fe2O3 60.28 2.86 2.01 1.35 1.14
MnO 1.51 0.74 0.67 0.00 0.03 0.05 0.02 0.00 0.00 0.00 0.03 MnO 0.08 0.07
MgO 2.80 1.08 12.66 0.01 0.00 0.00 0.01 0.12 0.03 0.00 0.02 MgO 15.61 14.28
CaO 0.01 0.02 0.02 7.97 6.63 0.54 0.00 0.01 0.02 0.01 0.03 CaO 0.01 0.01
Na2O 6.67 7.42 3.66 0.01 0.00 0.00 0.04 0.06 Na2O 0.63 0.33
JOURNAL OF PETROLOGY

K2O 0.89 1.02 10.50 0.02 0.02 0.00 0.07 0.05 K2O 9.10 9.39
Total 99.22 100.71 99.49 99.64 100.45 99.63 100.37 100.34 99.19 99.85 99.91 Total 96.21 96.21

Si 0.001 0.000 0.000 2.598 2.679 2.948 0.992 0.985 0.981 0.992 Si 5.308 5.259

1472
IV
Al 0.009 0.206 1.724 1.395 1.315 1.060 1.988 1.939 1.970 1.984 1.977 Al 2.692 2.741
T site 3.994 3.994 4.010 T site 8.000 8.000
VOLUME 45

VI
Ti 0.853 0.059 0.006 0.000 0.000 0.003 0.000 0.004 0.001 0.000 0.000 Al 0.271 0.098
Cr 0.000 0.003 0.004 0.000 0.000 0.000 0.001 0.001 0.001 0.002 0.000 Ti 0.585 0.867
Fe3þ 0.137 1.673 0.259 0.058 0.042 0.028 0.023 Cr 0.003 0.006
Fe2þ 0.998 0.976 0.474 0.008 0.003 0.014 0.016 Fe2þ 1.428 1.435
Mn 0.034 0.023 0.016 0.000 0.001 0.002 0.000 0.000 0.000 0.000 0.001 Mn 0.010 0.009
NUMBER 7

Mg 0.110 0.059 0.516 0.001 0.000 0.000 0.000 0.005 0.001 0.000 0.001 Mg 3.390 3.112
Ca 0.000 0.001 0.000 0.385 0.316 0.027 0.000 0.000 0.001 0.000 0.001 O site 5.688 5.528
Na 0.583 0.640 0.323 0.000 0.000 0.002 0.003 Ca 0.001 0.001
K 0.051 0.058 0.610 0.001 0.000 0.002 0.002 Na 0.177 0.092
JULY 2004

A site 1.028 1.019 0.976 K 1.692 1.751

XMn 0.033 A site 1.870 1.844
X(An) 0.378 0.312 0.028
X(Ab) 0.572 0.631 0.337 X(Mg) 0.704 0.684
X(Kf) 0.050 0.057 0.636

Ilmenite, magnetite, spinel, feldspar and biotite were normalized respectively to 3, 4, 4, 8, 22 oxygens. Corundum and aluminum silicate were normalized to 2 and
3 cations.

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 SASSI et al. ON THE FIBROLITE PROBLEM

TiO2 Fe3O4

MgAl2O4 FeAl2O4
FeTiO3 Fig. 6. Plot of pleonaste-rich spinels in terms of MgAl2O4–FeAl2O4–
ilmenite
Fe3O4 components (mole %). þ, pleonaste within or near biotite;
^, pleonaste associated with corundum or cordierite; ~, pleonaste

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Fe2TiO4 from sillimanite-rich domains.
ulvospinel

tita
no
ma
gn
eti
tes Or
Fe3O4
FeO magnetite Fe2O3
MM189
Kfs after Bt
Fig. 4. Ilmenite and magnetite compositions plotted in terms of TiO2–
FeO–Fe2O3. ~, ilmenite from green spinel- and biotite-bearing micro-
Kfs around And
domains (sample MM189); ~, ilmenite in K-feldspar-rich domains Kfs far from Bt
(sample CZ12); &, magnetite from sample MM189. Pl around And
Pl including fibrolite
Pl around Sill
950˚C
CZ12
850˚C
Kfs around Crd
Kfs associated
750˚C with melt inclusions

Ab An
Fig. 7. Feldspar compositions in different microstructural domains.
The ternary feldspar solvi at 750, 850 and 950
C, and 025 GPa, are
calculated according to Fuhrman & Lindsley (1988). Plagioclase com-
positions in contact with andalusite and sillimanite plot along the
750
C solvus curve, whereas the distribution of the data points of
plagioclase associated with fibrolite indicates a re-equilibration towards
the 950
C solvus.

Fig. 5. Exsolved ilmenite (Ilm) and spinel (Spl) lamellae parallel to

{111} in magnetite (Mag). Abbreviations after Kretz (1983).
moderate Ti content ranging from 006 to 008 a.p.f.u.
(analyses normalized to three cations), corresponding to
21–29 wt % TiO2. Mg ranges from 005 to 05 a.p.f.u.,
corresponding to 08–14 wt % MgO.
Figure 5 (sample MM189) shows ilmenite and
pleonaste spinel lamellae exsolved on {111} planes in
titanomagnetite. According to Buddington & Lindsley
(1964), ‘trellis-type’ exsolution such as that shown in
Fig. 5 could have formed by ‘oxidation–exsolution’ or
‘oxyexsolution’.
range 007–029 a.p.f.u. (analyses normalized to three
cations). XMg [Mg/(Mg þ Fe2þ)] ranges from 027 to
055. Higher XMg values are from grains within or near
biotite, whereas those with lower XMg are associated with
corundum or cordierite. Spinel from sillimanite-rich
domains has variable XMg from 027 to 055.
The Mg/Fe ratios in coexisting spinel and biotite have
been used to estimate the temperature of biotite decom-
position according to Brearley (1987). The KD [(Mg/
Fe)Spl/(Mg/Fe)Bt] values of samples CZ12 and MM189
range respectively from 027 to 029 and from 029 to
037, indicating temperatures from 815 to 845
C.

Green spinel Feldspar

Green spinel occurs in different microstructural domains Figure 7 shows the compositions of feldspar occurring in
as pleonaste (Fig. 6). Computed Fe3þ is always low, in the the different microstructural domains. Feldspar after

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 JOURNAL OF PETROLOGY
Fig. 8. Biotite compositional diagrams, showing (a) a nearly ideal trioctahedral phlogopite–annite solid solution, (b) small range of XMg values,
(c) deviation from the ideal tschermakitic (TK) and (d) Ti-vacancy (TV) substitutions. (See text for details.)
biotite has XOr 57–71%, XAb 28–41% and XAn 1–3%.
Away from biotite, feldspars are ternary solid solutions,
specifically having a more Ab-rich plagioclase composi-
tion (XOr ¼ 13–24%, XAb ¼ 61–70%, XAn ¼ 18–19%). In
leucocratic domains around andalusite relics (Fig. 2)
both plagioclase (XOr ¼ 4–9%, XAb ¼ 55–66%, XAn ¼
25–41%) and alkali-feldspar (XOr ¼ 66–69%, XAb ¼
31–33%, XAn ¼ 04–07%) occur. Plagioclase domains
in which sillimanite prisms crystallized have XOr 4–5%,
XAb 56–57% and XAn 37–38%, whereas feldspar within
which fibrolite nucleates is more alkali-rich (XOr 13–19%,
XAb 61–70%, XAn 15–19%). It should be noted that
plagioclase domains in contact with andalusite and silli-
manite plot along the 750
C ternary feldspar solvus
[calibration of Fuhrman & Lindsley (1988)], whereas
plagioclase compositions in contact with fibrolite plot
between the 850
C and 950
C solvi lines.
Alkali-feldspars occur also around melt inclusions and
within cordierite, having respectively XOr 60–61%, XAb
37–40%, XAn 012–016% and XOr 72–74%, XAb
25–27%, XAn 07–015%.
Corundum
Corundum is homogeneous and contains small amounts
of Fe3þ (002 a.p.f.u. analyses normalized to three
oxygens) within blue-coloured patches.
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VOLUME 45 NUMBER 7 JULY 2004
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Aluminium silicates
Andalusite has different Fe2O3 contents within the two
xenolith types (see Petrographic Features section). In the
sillimanite-free xenoliths, the Fe2O3 content of andalusite
is very low, ranging from 030 to 060 wt %, whereas in
the sillimanite–andalusite xenoliths, the pink andalusite
cores have Fe2O3 values of 27–29 wt %, and colourless
rims have 17–20 wt %. Sillimanite and fibrolite Fe2O3
contents are similar, ranging from 03 to 12 wt %.
The Fe2O3 content decreases from the andalusite
pink-coloured cores towards the colourless rims; this
might reflect either a change of redox conditions during
the growth of the andalusite rim or the lower Fe avail-
ability owing to the contemporaneous crystallization of
an Fe-rich mineral, such as biotite.
Biotite
Biotite compositions show a moderate deviation from
the ideal binary trioctahedral phlogopite–annite
K2(Fe,Mg)6(Al2Si6)O20(OH)4 series (Fig. 8a). No signifi-
cant compositional differences occur from core to rim.
Therefore, the different composition of biotite may reflect
the micro-chemical composition differences of the
nucleation sites. TiO2 content is very high, ranging
from a minimum of 440 to a maximum of 874 wt %
 SASSI et al. ON THE FIBROLITE PROBLEM

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Fig. 9. P–T pseudosection through the KNFMASCH system for the reference sample MM189 bulk composition. White arrow refers to the
regional HT/LP metamorphic evolution. The observed mineral assemblages constrain the P–T path to cross the Ms þ Qtz breakdown curve
(b) at pressures lower than the Al2SiO5 invariant point, along a nearly isobaric path. Black arrow refers to the sharp rise in temperature owing to
the pyrometamorphism. (1) HT–LP regional metamorphic climax; (2) maximum temperature experienced during pyrometamorphism. (a) And !
Sil; (b) Ms þ Qtz ! Kf þ Sil þ H2O; (c) Ms ¼ Kf þ Crn þ H2O; (d) Bt þ Crn ! Kf þ Spl þ H2O; (e) Bt þ Sil ! Kf þ Crd þ Crn þ Spl þ
H2O; (f ) Bt þ Crd ! Opx þ Kf þ Spl þ H2O.

(047–097 a.p.f.u; analyses normalized to 22 oxygens),

with most of the values (65% of the analyses) being higher
than 640 wt %. Titanium does not show any variation
with Si content. XMg values are relatively constant, ran-
ging from 066 to 072 (Fig. 8b). The biotites have a
moderate Na content ranging from 01 to 02 a.p.f.u.
corresponding to 031–10 wt % Na2O.
Figure 8c shows the VIAl deficiency and IVAl excess
with respect to the tschermakite substitution [IVSi,
VI
(Fe,Mg) $ VIAl, IVAl]. IVAl excess could imply a dif-
ferent substitution, i.e. an Fe-Tschermak substitution
[VI(Fe,Mg), IVSi ¼ VI(Fe3þ) þ IVAl]. The Ti content can
be explained by a Ti-Tschermak [VI(Fe, Mg) þ 2IV(Si4þ) $
VI
(Ti4þ) þ 2IV(Al)] and a Ti-vacancy [2VI(Fe,Mg) $
VI
(Ti4þ) þ VI(&)] substitution. Figure 8d shows that the
biotite compositions plot within a narrow band parallel to
the ideal Ti-vacancy substitution (arrow). Deviation of
biotite composition from the ideal Ti-vacancy substitu-
tion line may be due to contemporary substitutions that
promote Ti entry into octahedral sites, such as [2VIAl $
VI
Ti þ VI(Fe,Mg)] and [VIAl þ IVSi $ VITi þ IVAl]
(Dymek, 1983).
DISCUSSION
Metamorphic reaction sequences
Xenoliths MM189 and CZ12 display most of the petro-
graphic features described above and were selected as
representative samples for thermodynamic modelling.
Sample MM189 is an And–Sil–Pl–Kf–Crn–Bt–Spl–
Mag–Ilm assemblage; sample CZ12 is an And–Kf–
Crn–Bt–Spl–Crd–Mag–Ilm assemblage, i.e. it does not
contain Sil and Pl, but has Crd as an additional phase.
P–T pseudosections of the KNFMASCH (Fig. 9) and
KFMASH (Fig. 10) systems have been calculated by
means of the Vertex software package (Connolly, 1990),
on the basis of the bulk-rock compositions of samples
MM189 and CZ12. In calculating the pseudosections,
bulk chemical compositions were obtained by scanning
electron microscopy, scanning over a specific area of the
thin section, in which the previously mentioned mineral
assemblages had been determined optically and by scan-
ning electron microscopy. The bulk composition for
MM189 is (in wt %): SiO2 5328; Al2O3 2770, FeO
454, MgO 316, CaO 158, K2O 535 and Na2O 439,

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Fig. 10. P–T pseudosection through the KFMASH system for the reference sample CZ12 bulk composition. White arrow refers to the regional
HT/LP metamorphic evolution. The absence of sillimanite and the presence of andalusite indicate that pressure was lower than the intersection of
the muscovite breakdown reaction curve with the curve of the andalusite ! sillimanite pseudomorphic transformation, along a nearly isobaric
path. Black arrow refers to the sharp rise in temperature owing to the pyrometamorphism. (1) HT–LP regional metamorphic climax; (2)
maximum temperature experienced during pyrometamorphism. (a) And ! Sil; (b) Ms þ Qtz ! Kf þ And þ H2O; (c) Ms ¼ Kf þ Crn þ H2O;
(d) Bt þ And ! Kf þ Crd þ Crn þ Spl þ H2O.

and for CZ12 is SiO2 4534, Al2O3 3607, FeO 668,
MgO 247 and K2O 945.
The different mineral assemblages and microstructures
of the two samples indicate different reaction sequences
in rocks of similar bulk composition. The presence of
both in the same trachyte indicates that the two reaction
sequences relate to metamorphic P–T paths experienced
at different crustal levels during regional high-T–low-P
metamorphism, prior to their incorporation in the tra-
chytic magma. Thereafter the xenoliths were heated and
pyrometamorphosed by the magma so that their respect-
ive regional metamorphic parageneses were overprinted.
Regional high-T–low-P metamorphism
Sillimanite-bearing xenoliths (sample MM189)
These xenoliths are characterized by the presence of
andalusite and sillimanite, indicating that a set of reac-
tions producing Al2SiO5 occurred in both the andalusite
and sillimanite stability fields. The last of these reactions
probably relates to the breakdown of the muscovite þ
quartz þ plagioclase assemblage to produce sillimanite þ
K-feldspar þ melt. This constrains the P–T path to cross
the Ms þ Qtz breakdown curve (b in Fig. 9) within the
sillimanite stability field but at P lower than the Al2SiO5
invariant point.
The absence of quartz and the abundance of sillimanite
and K-feldspar in the rock indicates that quartz content
was relatively low in the protolith. Therefore, when
quartz was consumed in the above reaction, further mus-
covite decomposition could occur only at higher tem-
peratures (i.e. 630
C; c in Fig. 9). Andalusite, which is
always located within K-feldspar-rich plagioclase-bearing
biotite and spinel-free domains, metastably persisted
within the sillimanite stability field. However, it is invari-
ably embayed, indicating that it was resorbed by reaction
with a surrounding melt at high temperature. Sillimanite
preferentially nucleated in the muscovite-rich domains
rather than replacing andalusite, confirming the sluggish-
ness of this polymorphic transformation. The formation
of melt and the contemporaneous crystallization of
sillimanite in adjacent areas probably made the melt
corrosive to the metastable andalusite. Although a
general orientation of sillimanite prisms is evident, they
have irregular corroded margins indicating that, during
prograde metamorphism, a sillimanite-consuming reaction
occurred. Prismatic sillimanite, with small corundum
inclusions, is located within rectangular K-feldspar-rich,

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 SASSI et al. ON THE FIBROLITE PROBLEM

Table 2: Balancing of the fibrolite-producing reaction, normalized to

1 mole of reacting plagioclase

Pl 1 Kf 1 ! Pl 2 Kf 2 Sill
Vol. (cm3): 1.000 0.963 1.104 0.699 0.092
n, mol: 0.100 0.088 0.110 0.064 0.018

SiO2 2.581 2.987 2.805 2.970 0.997

TiO2 0.000 0.001 0.003 0.001 0.000
1.413 1.019 1.170 1.022 1.985

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AlO15
FeO 0.004 0.006 0.003 0.008 0.023
MnO 0.000 0.000 0.000 0.004 0.001
MgO 0.000 0.000 0.004 0.001 0.001
CaO 0.413 0.005 0.159 0.013 0.001
NaO0.5 0.561 0.290 0.689 0.418 0.003
KO0.5 0.043 0.671 0.240 0.579 0.002
Net reaction (n mol) 1.000 0.887 1.104 0.644 0.186

plagioclase-bearing and biotite-free domains that prob-
ably represent former sillimanite idioblasts rimmed by
a K-feldspar-bearing, biotite-free corona, with abundant
spinel and ilmenite. Outside these domains, biotite
occurs. This microstructural situation indicates that the
regional metamorphism reached peak conditions within
the Al2SiO5 þ biotite þ K-feldspar þ spinel þ corundum þ
ilmenite trivariant field (i.e. between d and e in Fig. 9).
At these regional metamorphic peak conditions, melt-
producing reactions were stopped by dehydration, and
the melt pools crystallized producing a K-feldspar, plagio-
clase and, locally, biotite aggregate.
Sillimanite-free xenoliths (sample CZ12)
Another group of rocks are characterized by the assem-
blage And–Kf–Crd–Spl–Crn–Bt–Mag–Ilm. In these
rocks also Al2SiO5 reactions occurred prior to their incor-
poration in the trachytic magma as xenoliths. The pre-
sence of nearly mono-mineralic andalusite bands suggests
that they represent former muscovite-rich, biotite-
bearing layers, where inclusion trails of spinel and ilme-
nite mark the orientation of a foliation. The andalusite
indicates that the muscovite þ quartz and the muscovite
breakdown reactions (respectively b and c in Fig. 10)
occurred in the andalusite stability field, and therefore
at pressures lower than those indicated by the intersection
of these reaction curves with that of the andalusite !
sillimanite transition (a in Fig. 10). Spinel and ilmenite
inclusion trails are also present within polygonal blasts of
K-feldspar and cordierite, indicating that their nucleation
was probably controlled by the presence of biotite. Small
elongated idioblasts of corundum along the foliation
and the absence of quartz in these xenoliths indicate a
quartz-poor protolith and that all available quartz was
consumed by the muscovite þ quartz reaction. Higher-
temperature breakdown of muscovite to form corundum
according to the reaction muscovite ! corundum þ
K-feldspar þ vapour is indicated by the small elongated
corundum idioblasts in inclusion trails and corundum
porphyroblasts within K-feldspar. With a further rise of
temperature ( 650
C), the andalusite þ biotite assem-
blage reacted to form K-feldspar þ cordierite þ spinel þ
ilmenite þ corundum (d in Fig. 10). The extent of anda-
lusite decomposition depends on the amount of biotite
present. Where biotite is abundant, andalusite is nearly
completely transformed into the higher-temperature
mineral assemblage, whereas when biotite is scarce,
andalusite is only partially replaced by corundum.
Pyrometamorphism
Sillimanite-bearing xenoliths: the formation of fibrolite
(sample MM189)
The incorporation of the xenoliths in the trachytic melt
caused an instantaneous rise of temperature. Ternary
feldspar thermometry (Fuhrman & Lindsley, 1988)
implies temperatures in the interval 750–950
C (Fig. 7).
However, our thermodynamic modelling suggests that
temperatures probably did not exceed that of the Opx-
in reaction ( f in Fig. 9), i.e. approximately 840
C, as Opx
has been never observed in the xenoliths. The range of
temperature estimates reflects the tendency of alkali-
feldspar and plagioclase to re-equilibrate at higher tem-
peratures in response to the increased solubility along the
feldspar solvus (Fig. 6), through a reaction such as
K-feldspar (1) þ plagioclase (1) ! K-feldspar (2) þ plagio-
clase (2) þ fibrolite. This reaction has been balanced
and calculations are shown in Table 2. The reaction is

1477
 JOURNAL OF PETROLOGY
confirmed by the common growth of fibrolite within
plagioclase in the presence of K-feldspar (Fig. 2d). Fibro-
lite also nucleates on sillimanite. At the same time, biotite
reacts to form K-feldspar þ spinel þ ilmenite, although
the formation of fibrolite is not related to this reaction,
because it never occurs in contact with biotite. Spinel–
biotite thermometry (Brearley, 1987) indicates tempera-
tures in the interval 815–845
C for this reaction. We
interpret that the growth of fibrolite is related to signific-
ant overstepping of the above-mentioned reaction invol-
ving feldspars. The extent of overstepping may have been
as much as 150
C, which is the difference between the
regional high-T–low-P metamorphic peak and the pyro-
metamorphic conditions. In the context of the biotite
breakdown reaction a second melting event occurred.
The small melt pockets that formed can be recognized
as small glass pools.
Sillimanite-free xenoliths: the formation of acicular
corundum (sample CZ12)
In these xenoliths, fibrolite did not form, the main reason
being the absence of plagioclase, so that the reaction
K-feldspar (1) þ plagioclase (1) ! K-feldspar (2) þ plagio-
clase (2) þ fibrolite could not occur. Although the strong
temperature rise during the pyrometamorphism prob-
ably resulted in a significant overstepping of the andalu-
site stability field, fibrolite also did not form, confirming
the sluggishness of this polymorphic transformation.
Instead, andalusite prisms are replaced by oriented tiny
fibrous corundum needles and K-feldspar.
Fibrolite growth as an effect of reaction
overstepping and anisotropic surface energy
The stability field of fibrolite relative to that of sillimanite
is a topic that continues to be controversial. The main
reason for this is that, because of the potential contribu-
tion of grain boundary energy to the total free energy
(Holdaway, 1971; Kerrick, 1990; Hemingway et al.,
1991), it is predicted that fibrolite should be stabilized
at higher temperatures than sillimanite (Kerrick, 1990;
Pattison, 1992). With the exception of a few cases (e.g.
Ahmad & Wilson, 1982; this study), it is observed that
fibrolite formation systematically precedes sillimanite
growth. This suggests that kinetic factors, rather than
epitaxy or metastability, control fibrolite growth.
When surface energy is considered as a contributor to
the overall Gibbs’ free energy of a newly forming mineral
assemblage, then it has to be balanced against other
sources of energy acting in the system, and it has to be
considered how these influence the reaction kinetics.
Heterogeneous reaction kinetics are directly correlated
to DG (Fyfe et al., 1958; Fisher & Lasaga, 1981), so that the
net rate (r) of a heterogeneous reaction can be expressed
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VOLUME 45 NUMBER 7 JULY 2004
as (Fisher & Lasaga, 1981)
r ¼ A exp ðEA =RT Þ½1  expðnDG=RT Þ ð1Þ
where A is a constant, EA is activation energy, R is
the gas constant, T is absolute temperature, n is some
number of the order of unity, and DG is the difference in
Gibbs’ free energy of the system in the actual state and in
the equilibrium state. Equation (1) shows that for any
forward reaction, the term involving DG yields a
progressive increase in r with rising T above the
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equilibrium boundary.
Because the effect of surface energy on chemical poten-
tials is very small in comparison with modest temperature
overstepping (Wheeler, 1991), surface energy will be an
important factor only when T is close to equilibrium.
Therefore, as long as a reaction temperature has been
overstepped, surface energy cannot dominate the system.
It should also be mentioned that acicular growth of a
mineral does not in itself imply high surface energy. The
surface energy of a crystal is dependent on the orientation
of a crystal surface relative to its lattice (Wheeler, 1991).
Therefore, if some faces have markedly lower energies
than others, these will be the most developed.
Another aspect of surface energy is that its contribution
to the total free energy may be reduced by changing the
shape of a growing crystal, because surface energy is pro-
portional to the surface area. However, for the growth of
larger crystals at the expense of long and thin ones, surface
energy must become a major driving force. This will be the
case only when fast reaction progress as a result of over-
stepping has brought the system back to equilibrium.
We therefore interpret that, when the reaction rate is
high because of overstepping, sillimanite forms strongly
elongate crystals (fibrolite) because the energy of the
{110} faces is low (Vernon, 1976) and their growth rate
is high. In this respect, fibrolite will always form
when a sillimanite-forming reaction has been significantly
overstepped, regardless of whether this occurs at the lower
temperatures of regional metamorphism or at the higher
temperatures equivalent to the central part of the
sillimanite stability field, as in the pyrometamorphosed
sillimanite- and fibrolite-bearing xenoliths. The same
seems to hold also for the growth of acicular corundum
pseudomorphing andalusite prisms, in the sillimanite-free
xenoliths.
ACKNOWLEDGEMENTS
The authors are greatly indebted to R. H. Grapes and
C. V. Guidotti for the thorough review of the manuscript.
F. P. Sassi is acknowledged for fruitful discussions and for
his critical reading of an earlier version of the manuscript.
Financial and analytical support have been provided by
the Istituto di Geoscienze e Georisorse (IGG-CNR).
 SASSI et al. ON THE FIBROLITE PROBLEM
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