J. metamorphic Geol.

, 1999, 17, 613–620

The assemblage stilpnomelane–chlorite–phengitic mica:

a geothermobarometer for blueschist and associated
greenschist terranes
K . L. C U R R IE A N D C . R . VA N S TA A L
Geological Survey of Canada, 601 Booth Street, Ottawa, Ontario, K1A OE8, Canada (kcurrie@nrcan.gc.ca)

ABSTRACT Two anhydrous equilibria can be written among the components of stilpnomelane, chlorite, white mica
and quartz, namely 89 daphnite+131 Fe-celadonite+190 quartz=96 stilpnomelane+71 muscovite, and
amesite+Mg-celadonite=muscovite+clinochlore. We assume that the free energy change of reaction,
DG=DGo+SRT lna j, is approximated by DG=A−BT +C(P−1)+SRT lna j, where DGo is the free energy
i i
change of the end-member components at temperature T and pressure P, a is the activity of component
i
i whose coefficient in the equilibrium is j, and A, B and C are constants to be determined. Values of C
can be approximated by the change in volume on reaction, namely C=406.517 J/bar for the first reaction
and C=0.613 J/bar for the second reaction. Constants A and B were determined by using six occurrences
of the assemblage stilpnomelane–chlorite–white mica for which P–T have been otherwise estimated. Using
solution models from the literature, linear regression gives for the first equation A=−6118.269 kJ, B=
−4584.09 J/K, and for the second equation A=19.397 kJ, B=66.72 J/K. These values predict P–T within
0.5 kbar and 25 K for all occurrences, and appear reasonably robust relative to probable analytical errors.
P–T are determined by intersection of the curves generated by given compositions in P–T space. Fine-
grained and/or zoned chlorite and white mica make application of the geothermobarometer difficult in
some instances, but our work in the Bathurst region of New Brunswick suggests that, with patience and
care, useful analyses can be obtained, and the database for the geothermobarometer greatly expanded.
Key words: blueschist; chlorite; geothermobarometry; stilpnomelane; phengite.

(Wager & Deer, 1939; Honegger et al., 1989) to granitic

I N T R O D U C T IO N
Stilpnomelane, a common mineral in rocks metamor-
phosed at low temperatures and moderate to high
pressures (Bucher & Frey, 1994, p 304), contains a
significant content of potassium, and occupies the
place of biotite in rocks where temperatures did not
reach biotite grade. Since the assemblage biotite–
chlorite–white mica–quartz can be used as a geother-
mobarometer (Powell & Evans, 1983; Bucher-
Nurminen, 1987), the analogous assemblage stilpnome-
lane–chlorite–white mica–quartz, which commonly
occurs in blueschist and greenschist facies assemblages,
may also yield useful information. This assemblage is
widely distributed in rocks of the Tetagouche and
Fournier groups of northern New Brunswick (van
Staal et al., 1990). We use new analytical data from
these rocks and data from the literature to show that
useful P–T information can be derived from stilpno-
melane-bearing assemblages, even though thermo-
dynamic data on stilpnomelane are lacking.
G EO L O G I C A L S ET T I N G
Stilpnomelane occurs in a variety of rock compositions
ranging from iron formation (Miyano & Klein, 1989)
through altered mafic and ultramafic igneous rocks
© Blackwell Science Inc., 0263-4929/99/$14.00
Journal of Metamorphic Geology, Volume 17, Number 6, 1999
rocks (Luchetti et al., 1990) and metamorphosed
sulphide ore deposits (Cook, 1993). Stilpnomelane
commonly occurs in an assemblage with chlorite and
quartz and either white mica or amphibole, but also
occurs in quartz-absent assemblages in mafic rocks
and sulphide ores. Stilpnomelane is a common mineral
within Ordovician felsic volcanic rocks and associated
massive sulphide deposits and iron formation of
northern New Brunswick, which were imbricated into
nappes during incorporation into the Brunswick
Subduction Complex (van Staal, 1987, 1994), a pro-
cess accompanied by low-temperature/high-pressure
regional metamorphism whose products vary from
sodic amphibole and pyroxene-bearing blueschists to
pumpellyite–actinolite or greenschist assemblages (van
Staal et al., 1990). The deformation history of these
rocks was polyphase, but only early, progressive,
thrust-related deformation, referred to as D , is relevant
1
to this paper. D outlasted peak metamorphism and
1
tectonically juxtaposed rocks that experienced different
metamorphic conditions. Characteristic mineral assem-
blages (for example sodic amphibole versus actinolite)
tend to be restricted to mafic rocks. Hence other
means are required to better constrain the regional
metamorphic conditions of numerous nappes located
within the felsic volcanic pile (Fig. 1) where intercalated
613
614 K. L . C URRI E & C. R. VAN S TA L

Fig. 1. Simplified geological map of the Bathurst region, northern New Brunswick, partly based on unpublished data of Rogers and
van Staal. The nappes shown form part of the Brunswick Subduction complex (van Staal, 1994). Sodic amphibole-bearing rocks
occur solely in the Canoe Lake and structurally higher nappes. The analysed stilpnomelane-bearing felsic rocks and intercalated
metabasalts occur in the Flat Landing Brook nappes near the tectonic boundary with the overlying nappes.

mafic rocks are rare or absent. Assemblages containing
stilpnomelane with chlorite, white mica, quartz, albite
and/or microcline, with accessory epidote, clinozoisite
or pumpellyite, show considerable promise for this
purpose. Stilpnomelane occurs in relatively low-strain
rocks as bow-ties or rosettes (Fig. 2a) that grew across
the earliest cleavage (S ) and folds (F ), and across
1 1
dynamically deformed quartz grains, or aggregates of
quartz grains. Quartz–quartz grain boundaries in these
aggregates are smoothly curved, and show no evidence
of adjustment to low-energy configurations with
stilpnomelane ( Vernon & Flood, 1977). In contrast,
stilpnomelane is commonly deformed and aligned in
high-strain phyllonites (Fig. 2b), and occurs as needles
or fibres in strain shadows and the necks of micro-
boudinaged feldspar porphyroclasts (Fig. 2c). These
microstructures, and consistent micro-kinking that
post-dates D (Fig. 2d), suggest that stilpnomelane
1
grew relatively late during subduction-related defor-
mation (post-dating peak pressures and formation of
the regional differentiated layering or domainal cleav-
age (S ) defined by phengite, chlorite, actinolite and/or
1
sodic amphibole) but before late D structures, such
1
as phyllonites, associated with out-of-sequence thrust-
ing (van Staal, 1994). On the basis of microstructures,
particularly stilpnomelane crosscutting S foliation and
1
associated folds, we interpret stilpnomelane to post-
date initial blueschist metamorphism, growing slightly
later as pressures declined but temperatures reached
or maintained near-peak values.
The literature on stilpnomelane suggests that similar
habits are common worldwide in high-pressure/low-
temperature metamorphic terranes. Brown (1975)
interpreted stilpnomelane in the Otago Schist of New
Zealand to form part of an equilibrium assemblage.
Miyano & Klein (1989) deduced a P–T stability field
for stilpnomelane ranging from about 300–470 °C and
up to 7 kbar. They considered the upper pressure limit
to be fixed by breakdown to zussmanite.
THE R M O D Y N A M I C B A S I S
Stilpnomelane, a group of minerals ranging from Fe2+-
dominant (ferrostilpnomelane) through Fe3+-dominant
(ferristilpnomelane) to Mg-dominant ( lennilenapeite)
or Mn-dominant (persettensite), forms a modulated
2:1 structure (Guggenheim & Eggleton, 1987) with
continuous octahedral sheets separated by modulated
tetrahedral sheets. The contents of potassium and
water show significant variation among analyses.
Brown (1971) proposed that low contents of potassium
are the result of post-crystallization leaching, and that
the oxidation of Fe observed in many specimens is
also a secondary phenomenon. In the Bathurst region
 STILPNOM ELANE–CHLOR ITE – MI C A GEOTHER MOB AR OMETRY 615

Fig. 2. Microstructures in stilpnomelane-bearing rocks of the Flat Landing Brook nappes.

(a) Rosettes of stilpnomelane cutting an F microfold of a vein in a red shale interlayered with metabasalt. (b) Aligned
stilpnomelane in a mafic rock with strong1S foliation. Local, partially preserved rosette-like structures suggest that alignment of
1
stilpnomelane is due to superimposed deformation. Note growth of stilpnomelane perpendicular to the walls of a late D
extensional vein. (c) D crenulation of stilpnomelane originally grown parallel to S and L . Stilpnomelane grew in part 1in
intergranular veins and2 pressure shadows of a D boudinaged feldspar porphyroclast 1 shortened
1 during D . (d) D micro-kinking of
stilpnomelane rosettes accompanied by new growth 1 along kink band boundaries. 2 2

of New Brunswick, brown, oxidized stilpnomelane and

tends to occur near or within veins, and contains
preserved patches of green, reduced material, support-
ing the hypothesis of Brown (1971) that ferristilpnomel-
ane formed by late oxidation of ferrostilpnomelane.
We therefore analysed only green stilpnomelane. We
adopt a formula for end-member ferrostilpnomelane
of K Fe Si AlO (OH) ·1.521H O , identical to
0.625 6 8 21 5.625 2
that proposed by Eggleton & Chappell (1978), except
for the content of ‘zeolitic’ water, a variable which
depends on the protonization of the hydroxyl groups.
The assumed value, 1.3% larger than the value of
1.500 used by Miyano & Klein (1989), but well within
the range of natural analyses, permits an anhydrous
reaction to be written involving stilpnomelane, chlorite,
phengitic mica and quartz, thus avoiding complexities
involving the fugacity of water.
Consider the equilibria
89 daphnite+131 Fe-celadonite+190 quartz
=96 stilpnomelane+71 muscovite (1)
amesite+Mg-celadonite=clinochlore+muscovite
(2)
At equilibrium, free energies on opposite sides of the
equilibria are identical. Denoting the difference between
the free energy of the right and left sides of the
equilibria as DG, this requires
DG=DGo+RT lnK=DGo+SRT lna j=0
i
where DGo is the free energy change for the pure end
members at temperature and pressure T and P, K is
the equilibrium constant, a is the activity of component
i
i whose coefficient in reaction (1) is j, and R is the gas
constant (8.3143 J/K/mol ). For anhydrous equilibria,
DGo can generally be well approximated in the form
A−BT +C(P−1) where A, B and C are (approxi-
mately) the changes on reaction in enthalpy of
formation, entropy and volume at 298 K, 1 bar. We
therefore assume that equilibria (1) and (2) plot in
616 K. L . C URRI E & C. R. VAN S TA L

P–T space as lines of form for equilibrium of reaction (1) is

A−BT +C(P−1)+SRT lna j=0
i 1
This formulation ignores changes in heat capacity,
compressibility and thermal expansion terms, assuming
that they cancel on opposite sides of the reaction.
Molar volumes listed in Table 1 give C=406.517 J/bar
for equilibrium (1) and C=0.613 J/bar for equilib-
rium (2).
In order to be applied to actual compositions,
activities must be calculated for the components of
equilibria (1) and (2). Activity models used in this
work are listed in Table 1. For stipnomelane we follow
Miyano & Klein (1989) and assume ideal ionic
solution, ignoring the content of potassium. This
formulation amounts to assuming that all analysed
stilpnomelane originally contained the stoichiometric
amount of potassium.
For white mica we use the model of Holland &
Powell (1998) which involves ideal mixing of units in
which each Mg or Fe atom in the tetrahedral sheet
has only Al for nearest neighbours, a configuration
assured by permitting Al to mix with (Fe,Mg) on only
one of the two dioctahedral sites. In this model, Al
mixes with Si on two of the four T sites. Holland &
Powell (1998) note that while the model gives reason-
able agreement with most experiments, it does not
give a good fit with experimental data for the
talc+muscovite breakdown. However, the alternative
subregular solution model of Massonne (1995) contains
numerous parameters which are poorly constrained by
experimental data.
For chlorite we use the solution model outlined by
Holland et al. (1998), which incorporates non-ideal
solution, together with modified solution parameters
recently published on the internet (October 1998) at
www.esc.cambridge.ac.uk/astaff/holland/ds5/chlorites,
see also Table (1). Holland et al. (1998) note that
calibration of the non-ideality is difficult, and may
need modification, especially for iron-rich chlorite.
Incorporating activity terms explicitly, the condition
(3) A −T B +RT (71lna +96lna −89lna
1 m stp da
−131lna )+406.517(P−1)=0 (4)
f
while the condition for equilibrium of reaction (2)
becomes
A −T B +RT [ln(a /a )+ln(a /a )]
2 2 ms f cl am
+0.613(P−1)=0 (5)
where the subscripts refer to components as follows:
ms, muscovite; stp, stilpnomelane; da, daphnite; f,
Fe-celadonite; cl, clinochlore; am, amesite; g, Mg-
celadonite.
EX T R A C T ION OF C O N S TA N T S
For an occurrence of stipnomelane+chlorite+white
mica+quartz with mineral compositions known, and
P and T of formation estimated by other means, Eqs
(4) and (5) reduce to two linear expressions involving
the unknown constants A , B , A and B . We have
1 1 2 2
used new data from greenschist facies rocks of the
Bathurst region of New Brunswick and five examples
drawn from the literature (Table 2) to estimate these
constants. For literature data, estimates of P–T given
by the references were used, except that we used
estimates of Yardley (1982) for data from the Otago
Schist of New Zealand given by Brown (1975). P–T
estimates for the East Karkonosze complex
(Smulikowski, 1995) and Paikon series (Baroz et al.,
1987) are not precise, but both are stated to contain
biotite+stilpnomelane and therefore temperatures
were probably above 400 °C. The sample from the
Bathurst region is unusually favourable for calibration
because it contains K-feldspar, and is intercalated with
mafic schists. We estimated P–T from two-feldspar
geothermometry (Whitney & Stormer, 1977) on patch
perthites, and from intercalated mafic schists with the
assemblage greenish-blue sodic actinolite–chlorite–
epidote–albite (compositions given in Table 3). The

Table 1. Thermodynamic properties of

Volume mineral components of the assemblage
Component Composition J/bar Activity stilpnomelane–chlorite–white mica.
Stilpnomelane K Fe Si AlO (OH) ·1.521H O 37.539 x6 ·x ·x8
0.625 6 8 21 5.625 2 Fe Al Si
Daphnite* Fe Al Si O (OH) 21.340 4x5(1−y+N)( y+N)(1−y)y
5 2 3 10 8
Clinochlore* Mg Al Si O (OH) 21.090 4(1−x)5(1−y+N)( y+N) (1−y)y
5 2 3 10 8
Amesite* Mg Al Si O (OH) 20.520 (1x)4( y−N)( y+N)y2
4 4 2 10 8
Fe-celadonite KFeAlSi O (OH) 14.300 x ·x ·x2
4 10 2 K Fe Si
Mg-celadonite KMgAlSi O (OH) 14.040 x ·x ·x2
4 10 2 K Mg Si
Muscovite KAl Si O (OH) 14.083 4·x ·x ·x ·x
3 3 10 2 K Al Al Si
Quartz SiO 2.269 1.0
2

Formula, volume and activity of stilpnomelane from Miyano & Klein (1989). Other data from Holland & Powell (1998).
* Only the ideal part of the activity is given. x=(Fe/Fe+Mg), y=xT2 and N=(xM4−xM1 in chlorite. In the model of
Al Al Al
Holland et al. (1998), the non-ideal part of the chlorite activity is calculated from a hypothetical quaternary solution
among clinochlore, amesite, daphnite and Al-free Mg-chlorite (af ) according to the following formulae: RT lnc =
cl
p (1−p ) W +p (1−p ) w +p (1−p ) w −p −p −p RT lnc =p (1−p )
am cl afam af cl afcl da cl clda afpamwafam dapafwafda ampdawamda da af da
W +p (1−p ) w +p (1−p ) w −p −p −p RT lnc =p (1−p ) W +p (1−p )
afda am da amda cl da clda afpamwafam clpafwafcl ampclwclam am af am afam cl am
w +p (1−p ) w −p −p −p where p =y−N, p =1−y−N, p =2x(3−y)/5 and p =
afcl da am amda afpclwafcl dapclwclda afpdawafda am af da cl
2N−2x(3−y)/5 . w =18 kJ, w =20 kJ, w =18 kJ, w =2.5 kJ, w =14.5 kJ and w =13.5 kJ . See Holland
afcl afam clam clda afda amda
et al. (1998) for details.
 STILPNOM ELANE–CHLOR ITE – MI C A GEOTHER MOB AR OMETRY 617

Table 2. Compositions of co-existing stilpnomelane, chlorite and phengitic mica.

Bathurst Skookum Gulch East Otago West Otago

1 2 3 kf pl 1 2 3 1 2 3 1 2 3

SiO 46.10 26.60 51.70 63.92 68.28 46.40 27.44 54.91 48.30 28.20 51.30 45.80 28.60 52.76
2
TiO 0.01 0.10 0.16 n.d. n.d. n.d. n.d. n.d. 0.08 0.00 0.18 0.00 0.00 0.00
2
Al O 6.06 18.09 22.83 18.43 19.06 6.37 18.64 21.42 6.33 19.10 26.80 6.30 18.00 23.66
2 3
FeO† 29.15 26.41 5.24 0.07 0.10 28.86 25.49 4.34 31.70 32.90 4.73 29.50 29.80 5.67
MnO 0.45 0.34 0.07 n.d. n.d. 1.61 0.58 0.00 1.21 0.57 0.05 0.91 0.39 0.04
MgO 6.94 12.41 3.30 0.00 0.00 7.23 14.84 5.05 5.22 10.60 3.03 7.22 12.50 3.19
CaO 0.15 0.07 0.03 0.00 0.08 0.36 0.20 0.15 0.31 0.00 0.00 0.52 0.36 0.01
Na O 0.02 0.01 0.03 0.21 12.23 0.03 0.11 0.06 0.03 0.00 0.13 0.01 0.03 0.16
2
KO 1.29 0.06 10.21 15.37 0.10 0.79 0.09 10.31 0.76 0.00 10.80 0.25 0.01 10.72
2
Total 90.17 84.08 93.57 99.16* 99.85 91.65 87.39 96.24 93.94 91.37 97.02 90.51 89.69 96.21
Si 7.895 2.948 3.556 2.991 2.995 7.822 2.907 3.647 7.979 2.947 3.364 7.809 3.003 3.541
Ti 0.001 0.008 0.008 0.000 0.000 0.000 0.000 0.000 0.010 0.000 0.009 0.000 0.000 0.000
Al 1.223 2.363 1.856 1.017 0.987 1.266 2.327 1.676 1.232 2.352 2.071 1.266 2.228 1.872
Fe 4.175 2.448 0.301 0.003 0.004 4.069 2.258 0.241 4.379 2.875 0.258 4.206 2.617 0.318
Mn 0.065 0.032 0.004 0.000 0.000 0.230 0.052 0.000 0.169 0.050 0.003 0.131 0.035 0.002
Mg 1.772 2.050 0.338 0.000 0.000 1.817 2.344 0.500 1.298 1.651 0.296 1.835 1.957 0.319
Ca 0.028 0.008 0.002 0.000 0.004 0.063 0.023 0.011 0.055 0.000 0.000 0.095 0.041 0.001
Na 0.007 0.002 0.004 0.019 1.040 0.010 0.023 0.008 0.010 0.000 0.017 0.003 0.006 0.021
K 0.282 0.008 0.896 0.918 0.006 0.170 0.012 0.873 0.160 0.000 0.903 0.054 0.001 0.918
Ions 15.448 9.867 6.965 4.969* 5.000 15.447 9.946 6.956 15.292 9.877 6.922 15.400 9.887 6.992
Charge 47.625 28 22 16 16 47.625 28 22 47.625 28 22 47.625 28 22
T (K, estimate) 623 548 663 663 723
P ( kbar, estimate) 6.0 7.0 4.6 6.4 6.0

lnK 244.415 245.933 286.927 177.530

1
lnK ∞ 78.647 88.016 74.472 39.210 98.606
1
lnK 2.6305 2.0300 3.0217 3.1001 3.1009
2
lnK ∞ 0.8871 0.8352 0.9252 0.5734
2
T (K, calculated) 618 553 658 638 704
P ( kbar, calculated) 6.02 7.03 4.77 6.04 5.59

E. Karkonosze Paikon series

1 2 3 1 2 3

SiO 45.1 25.32 50.30 50.51 26.39 51.86

2
TiO 0.04 0.12 0.12 0.00 0.00 0.00
2
Al O 6.09 18.12 25.23 6.41 20.68 26.24
2 3
FeO† 28.91 32.17 7.13 21.47 23.55 4.37
MnO 1.03 0.27 0.00 0.63 0.16 0.04
MgO 6.18 9.63 2.42 11.54 16.96 2.91
CaO 0.26 0.09 0.00 0.05 0.02 0.01
Na O 0.09 0.06 0.09 0.22 0.00 0.00
2
KO 0.82 0.03 8.66 1.32 0.00 10.25
2
Total 89.23 85.81 93.94 92.16 87.76 95.68

Si 7.928 2.847 3.384 8.064 2.747 3.426

Ti 0.005 0.010 0.006 0.000 0.000 0.000
Al 1.242 2.401 2.000 1.206 2.537 2.043
Fe 4.184 3.025 0.401 2.867 2.050 0.242
Mn 0.151 0.026 0.000 0.085 0.014 0.002
Mg 1.594 1.614 0.243 2.747 2.632 0.287
Ca 0.048 0.011 0.000 0.009 0.002 0.001
Na 0.030 0.013 0.012 0.068 0.000 0.000
K 0.181 0.004 0.743 0.269 0.000 0.864
Ions 15.364 9.951 6.789 15.314 9.984 6.865
Charge 47.625 28 22 47.625 28 22

T (K, estimate) 723

P ( kbar, estimate) 4.5

lnK 203.923 286.397

1
lnK ∞ 92.594
1
lnK 3.2972
2
lnK ∞ 1.0251 1.0404
2
T (K, calculated) 723
P ( kbar, calculated) 4.54

Data sources: Skookum Gulch Cotkin (1987); Bathurst, see text, van Staal et al. (1990); van Staal, unpublished data; East Otago and West Otago Brown, 1975; East Karkonosze
Smulikowski, 1995; Paikon series Baroz et al., 1987; P–T estimates from Yardley, 1982. Symbols used: 1, stilpnomelane; 2, chlorite; 3, phengite; kf, potassium feldspar; pl, plagioclase.
* Includes 1.16% BaO, which gives 0.021 atoms Ba in the standard cell. † Total Fe as FeO. lnK and lnK give the ideal part of the equilibrium constant. lnK∞ and lnK∞ give the non-
1 2 1 2
equilibrium part, −89RT lnc for equilibrium 1 and RT (lnc −lnc ) for equilibrium 2. The two parts are added to give the complete constant.
da cl am
618 K. L . C URRI E & C. R. VAN S TA L

Table 3. Composition of minerals from metabasalt intercalated

with analysed stilpnomelane-bearing felsic rocks, Bathurst,
New Brunswick.
Amphibole Epidote Chlorite Albite

SiO 53.27 38.35 27.91 66.97

2
Al O 2.14 21.56 17.83 19.34
2 3
FeO* 16.03 14.46 24.37 0.19

P (kilobar)
MnO 0.52 0.36 0.75 0.04
MgO 13.04 0.00 16.62 0.03
CaO 9.87 23.36 0.15 0.10 606K
Na O
2
1.81 0.00 0.00 11.76 6.02 kbar
KO 0.15 0.00 0.00 0.05
2
Total 96.49 98.09 87.62 98.47

Si 7.852 3.032 2.932 2.977

Al 0.371 2.009 2.207 1.013
Fe3 0.000 0.927 0.000 0.007
Fe2 1.976 0.029 2.141 0.000
Mn 0.068 0.024 0.067 0.001
Mg 2.865 0.000 2.602 0.002
Ca 1.558 1.979 0.016 0.005
T (K)
Na 0.516 0.000 0.000 1.013
K 0.028 0.000 0.000 0.003
Ions 15.234 8.000 9.962 5.021
Fig. 3. P–T estimates from the assemblage stilpnomelane–
Charges 46 25 28 16 chlorite–phengitic mica-quartz for the Bathurst region. Box
shows the P–T estimates derived from other data (see text, van
* Total iron as FeO. TiO searched for but not found. Ferric iron calculated by reducing
2
Staal et al., 1990). The size of the shaded box approximates the
epidote analysis to 8 ions, and albite towards 5.000. minimum uncertainty of estimate (±25 K±0.5 kbar). The
positions of equilibrium 1 (labelled S) and equilibrium 2
(labelled P) are shown. Note the high angle of intersection.
epidote composition, in the absence of pumpellyite, The position of the equilibrium 6 microcline+clinochlore+2
suggests temperatures near 350 °C (Banno, 1998; Brown quartz+2 water=5 celadonite+muscovite (labelled M) was
& O’Neil, 1982), in agreement with two-feldspar temper- calculated from the Berman (1988) database supplemented by
atures. Application of the program of Berman (1991) compatible data from Massonee (1995). Curve T shows the
position of the equilibrium 6 clinozoisite+7 quartz
and the database of Berman (1988) to the reaction +clinochlore=10 anorthite+tremolite+6 water, calculated
clinochlore+6 clinozoisite+7 quartz=tremolite+10 from the data in Table 3. The curve labelled F is the two-
anorthite+6 water gives a curve which passes through feldspar temperature from the Whitney & Stormer (1977)
350 °C at 5.9 kbar (assuming unit activity of water). We two-feldspar thermometer (xpl =0.912, xks =0.022).
ab ab
have assumed values of 350 °C, 6.0 kbar for this
occurrence, essentially identical to the values deduced Applied to the data of Table 2, Eqs (6) and (7)
by van Staal et al. (1990; unpublished data) from estimate P–T well within the bounds quoted by the
mineral assemblages in surrounding rocks. The semi- original authors, falling within 25 °C and 0.5 kbar of
empirical amphibole calibration of Triboulet (1992) the data points. The estimates also fall generally within
gives a somewhat higher pressure estimate of 6.5 kbar. the stability range of stilpnomelane proposed by
Application of Eqs (4) and (5) gives two sets of six Miyano & Klein (1989) of 300–470 °C and up to
equations in two unknowns. Denoting the correlation 7 kbar. Our calculated results range from 280 to 450 °C
coefficient by r, linear regression gives A =−6 118 269, and 4.6–7.0 kbar. Miyano & Klein (1989) suggested
1
B =−4584.09, r =0.8450, A =19397, B =66.72 and that at higher pressures stilpnomelane would break
1 1 2 2
r =0.9852. Given these constants, Eqs (4) and (5) down to zussmanite, but reaction (1) suggests that the
2
reduce to linear expressions in P and T ubiquitous assemblage chlorite+white mica is a more
likely high-pressure equivalent of stilpnomelane. We
−6118269−89RT lnc +(RlnK∞ +4584.09) T
da 1 have written a small BASIC program which calculates
+406.517(P−1)=0 (6)
T and P using Eqs (6) and (7) and analyses of
and stilpnomelane, chlorite and phengitic mica reduced as
in Table 2. This program is available from the authors
15434+RT ( lnc −lnc )+(RlnK∞ −52.85) T
cl am 2 on request.
+0.613(P−1)=0 (7)
In order to assess the sensitivity of the derived
where lnK∞=SRT lnia j (ia being the ideal activity as values to analytical errors, we varied X and X for
i Mg Fe
listed in Table 1), RT lnc the non-ideal contribution to the input minerals by 0.02 (increasing one and
i
the activity (also listed in Table 1); subscripts 1 and 2 decreasing the other). We also examined the effect of
refer to reactions (1) and (2). The intersection of the Tschermak’s substitution (2Al=Si+[Fe,Mg]) by vary-
two lines in P–T space gives an estimate of P–T for ing Al by 0.02 with compensating changes in Si, Fe
the assemblage. The intersection is well defined because and Mg. None of these changes varied the predicted
the first expression has a moderate negative slope temperature by more than 20 K or pressure by more
while the second has a steep positive slope, assuring a than 0.5 kbar. We conclude that the predicted P–T are
high-angle intersection, as ilustrated in Fig. 3. reasonably robust against analytical uncertainties.
 STILPNOM ELANE–CHLOR ITE – MI C A GEOTHER MOB AR OMETRY
Eq. (7) shows that at constant pressure, the mol
fraction of celadonite in white mica decreases with
increasing temperature. However, at constant tempera-
ture, the appearance of phengitic mica, relative to
the equivalent lower-pressure assemblage K-feldspar+
chlorite+quartz depends on pressure. We used the
program TWQ (Berman, 1991) augmented by data for
celadonite, extracted by Massonne (1995) to be
compatible with this database, to calculate the position
of the equilibrium
6 microcline+clinochlore+2 quartz+2 water
=5 celadonite+muscovite
for rhyolitic rocks of the Bathurst camp which contain
the assemblage microcline (0.98 KAlSi O )–quartz–
3 8
white mica–chlorite–stilpnomelane. The results are in
good agreement with other P–T estimates (Fig. 3). If a
(fictive) composition of microcline of the composition
observed in the stilpnomelane-bearing rocks of the
Bathurst area is assumed, this equilibrium gives
estimates of minimum pressure for the other six
occurrences of coexisting phengite and chlorite. These
estimates lie 0–2 kbar below pressures calculated from
the stilpnomelane–chlorite–phengite assemblage, sug-
gesting that the stability field of stilpnomelane lies
near the lower pressure limit for the stability of
phengitic mica (Si >3.35 atoms/unit cell ).
D IS C US SI ON
Accurate estimation of metamorphic temperature for
blueschist and associated greenschist facies rocks is
notoriously difficult. The estimates upon which our
empirical calibration is based are thus less reliable
than would be desirable, although the ordering with
respect to temperature and pressure is probably
reliable. A geothermobarometer based on an internally
consistent thermodynamic dataset such as that of
Berman (1988) or Holland & Powell (1998) would be
highly desirable, but the necessary experimental data
do not exist for stilpnomelane, and will not be available
in the foreseeable future. The database of Holland &
Powell (1998) contains entries for celadonite, amesite,
muscovite and clinochlore. We have calculated
the change in free energy for end members for the
reaction amesite+celadonite=muscovite+clinochlore
using the expressions for heat capacity, thermal
expansion and bulk modulus as given by Holland
& Powell (1998) and numerical data from
THERMOCALC 2.7 (posted on the the internet at
www.esc.cam.ac.uk/astaff/holland/thermocalc, October
1998). At 350 °C, 6.0 kbar, DGo=−29.740 kJ. The
approximation DH −T DS +PDV =−17 500
298 298 1298
−25.50T +0.613P gives −29.708 kJ, suggesting that
the linear approximation is reliable for this reaction.
The value of lnK required for equilibrium at 343 °C,
2
6.02 kbar is 5.763(−D G°/RT ). lnK for the Bathurst
2
sample at this P–T is 2.6305+4543/RT , a discrepancy
619
in lnK of 2.247 at 343 °C. This discrepancy corre-
2
sponds to 11.508 kJ (RT DlnK ), equivalent to 18.8 kbar
2
(11508/0.613) in pressure or 55 °C (11508/25.5R) in
temperature. The size of the discrepancy, emphasized
by the differences between the sign and magnitude of
DH and DS calculated from the tabulation of
298 298
Holland & Powell (1998) and the values of A and B
2 2
deduced by us from natural occurrences, decreases
with increasing temperature, reaching zero near 900 °C.
The discrepancy presumably results from inadequate
solution models for chlorite and/or phengite. Whatever
the cause, the large discrepancy at blueschist–greensch-
ist conditions precludes use of the entropy and enthalpy
tabulations of Holland & Powell (1998) for the
estimation of A and B .
2 2
A stilpnomelane–chlorite–phengite assemblage lack-
ing quartz was reported by Hoffman & Keller (1979)
from the island of Milos. Our proposed geothermo-
barometer involves quartz, and is thus not applicable
to this assemblage. Application regardless of assem-
blage predicts a temperature above 400 °C, clearly too
high for this lawsonite-bearing assemblage. We con-
clude that application of the geothermobarometer
should be restricted to quartz-bearing assemblages.
The present study shows that minerals such as
stilpnomelane can be used for geothermobarometry
even when their stoichiometry and structure are not
well-known, as long as reliable P–T conditions for
their formation can be defined. At first sight, ignoring
heat capacity, compressibility and thermal expansion
terms in the thermodynamic analysis appears to be a
severe objection. However, corrections introduced by
these terms are commonly small for anhydrous reac-
tions, and the approximation has generally been found
to be reliable, if sometimes crude. In principle, it would
be possible to obtain two other P–T lines from the
assemblage stilpnomelane–chlorite–white mica using
the Mg analogue of stilpnomelane and the iron
analogue of amesite (pseudothuringite). However, the
volumes of Mg-stilpnomelane and pseudothuringite
are imperfectly known, so that the method used here
cannot produce useful information.
Microstructures suggest that stilpnomelane grew on
the decompression part of the P–T path, and therefore
may give a reasonable estimate of peak temperature,
but only provides a minimum value for peak pressure.
For most compositions, stilpnomelane indicates
decompression assemblages requiring minimum tem-
perature above c. 250 °C and pressure below c. 8 kbar.
For some relatively unusual Fe-rich and Al-poor
compositions, such as iron formation, stilpnomelane
may form at significantly lower temperatures on the
prograde path (compare Kaufman, 1996). In principle,
stilpnomelane in basaltic compositions could be used
in a similar fashion to that outlined here, via reactions
such as
81 actinolite+159 K-feldspar+343 quartz+186 water
=200 stilpnomelane+81 epidote
620 K. L . C URRI E & C. R. VAN S TA L
However, other better-calibrated reactions are com-
monly available for basaltic compositions. We therefore
suggest that stilpnomelane geothermobarometry will
be most useful for granitoid compositions.
Stilpnomelane–chlorite–phengite assemblages have
been reported in virtually all blueschist terranes of the
world, but suitable analytical data to extend the
database for the geothermometer are sparse, probably
because of the fine-grained, intergrown, possibly
inhomogeneous nature of the chlorite and white mica
associated with stilpnomelane, which commonly makes
it difficult to obtain acceptable analyses for these
minerals and to demonstrate that they are in equilib-
rium. On the basis of our work in the Bathurst region,
we believe that, with patience and care, useful analyses
can be obtained, and the database for more robust
calculation of the geothermobarometer greatly
expanded. The reliability of the geothermobarometer
can only be assessed by further application.
A C K N O W LE D G E M E N T S
R. Powell, E. H. Brown, R. G. Berman and T. J. B.
Holland gave helpful criticism and suggestions.
This manuscript is Geological Survey of Canada
Contribution 1998207.
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Received 27 April 1998; revision accepted 15 February 1999.