(Mg..754Fe..246)SiO3

Sci.
Repts.
Yokohama
Nail.
IIigh
Univ.,
II, No.
Sec.
Aluminous
34, p･
Orthopyroxene
for
irL the
quartz
Stability
the
Granulite
1987･
itL the
10
at
(Mg..754Fe..246)SiO3-Al203
Implications
October,
31-39,
15
and
Join
kb&r:
Orthopyroxene･Bpinel･
of
F&cies
Rocks
M■etamorphic
By
ARIMA*
Makoto
Abstract.
The
solubility
of
(Mgo.754Feo.246)SiO3-A1203has
of 950-1200oC
orthopyroxene
with
previously
stable
the
under
it coexists
splnel,
with
in
and
increases
quartz
suggest,
combined
with
are
splnel-quartz
and
of
conditions
Fe2＋-rich rock
the
orthopyroxene,
coexisting
would
that
splnel,
an
in
content
alumina
the highest
at
reach
starting
compositions･
more
1t is inferred
and
sapphirine,
of
pbase五eld
＋
＋spinel
(ss)
(ss)
different
between
granulites
range
single
spinel
results
pressure
stable
occurrences,
natural
with
join
the
of
part
temperature
a
of
sapphirine-quartz
relations
in sapphirine-quartz
orthopyroxene
that
a
a
of ortbopyroxene
coexisting
The
present
and
is
partitioning
in the
sapphirine
data,
splneトqnartz
consists
assemblage
temperature
same
where
Mg-Fe2＋
Considering
an
pressure.
and
experimentally
join studied
of orthopyroxene
experimental
published
compositions,
The
(ss) and
solid solution
content
alumina
temperature
increaslng
in
in
determined
kbar.
15
and
The
quartz.
and
10
at
orthopyroxene
in
alumina
been
value
vben
quartz.
Introductiom
The
stability of high
those
who
ma丘c
xenoliths.
pyroxenes
coexistlng
and/or
With
often
splnel,
high
extremely
temperatures
estimated
for
1983).
and Barnett,
during
metamorphism
The
Barnett,
experimental
studies
sapphirine,
cordierite,
1983).
temperatures
indicators
the
Land,
*
petrologlCal
Antarctica
stability
and
Institute,
could
Seifert,
Seifert,
study
(Grew,
of aluminous
Geological
and
be
1981).
on
1980)
experimental
from
suggest
National
that
an
the
University,
rocks,
ortho-
low
corundum
water
activity
Arima
(ex.
solubility
is
and
in orthoat
quartz
Arima
(ex.
%)
and/or
various
pressure
and
and/or
temperature
1976;
Arima
and
study
Napier
by
signincant
In this paper
ultra-
of alumina
pressure
Holdaway,
granulites
ortbopyroxene.
Yokohama
used
The
solubility
alumina
as
IOwt.
the
solubility
Yokohama,
Onuma,
Holdaway
Complex,
effect
240
to
derived
sillimanite,
granulites
sillimanite
1972;
pelitic
and
the
the
on
that
suggest
and
(Anastasiou
1977 ; Annersten
been
pressures
and
dependences
temperature
and
The
coexisting
pyroxene
relatively
have
mantle
cordierite,
Al203
(up to
high
interest
considerable
rocks
and
metamorphic
facies
metamorphosed
sapphirine,
contain
is of
orthopyroxene
facies
granulite
In the granulite
study
quartz
aluminous
(1976)
Enderby
of Fe2十on
of alumina
Japan.
the
in
M.
32
orthpopyroxene
at
coexists
with
orthopyroxene
studied,
10 and
of 95011200oC
range
15kbari
splnel
and
Experimental
High
pressure
and
of 1.25cm
sodium
in
chloride-talc-high
Temperature
mediums.
pressure
dependence
pressure
calibration
of
(1969). Synthetic
oxide
are
as
sample
by
the
done
were
the
The
same
diffraction
are
results
identi丘ed
crystals,
euhedral
in
by
and
Based
rounded-shap.
15kbar
were
determined
or
of
part
A
join
the
three
part
alumina-enriched
at
various
T-Ⅹ
in
alumina
dependence
and
and
Onuma,
is higher
splnel
in
material.
hercynlte
splnel
the
with
quartz
in
and
at
the
size with
shown
single
sections
the
that
run
was
splnel
10 and
et
al.
materials.
for 6hrs,
v▲ere
examined
used
optically
and
in
and/or
magnetite
content
green
product
estimated
indicate
and
15kbar
pressure
with
colour,
lOOOoC
and
orthopyroxene
based
lOwt.
Comparingthe
suggestlng
that
in
they
diffraction
exhibit
(Arima
in
relative
alumina
sapphirine
system
determined
%
present
with
Fe-free
the
X-ray
pressure
positive
coexisting
in
of
increaslng
with
the
the
on
solubility
incorporates
(Fig. 1). A
10kbar
relatively
in
the
increaslng
The
the
that
suggest
in orthopyroxne
system
observed.
in
increases
quartz
poor
alumina
graphically
orthopyroxene
components.
at
alumina
and
was
orthopyroxene
of
10
at
sections
occurs
forms
rectangular-
relatively
orthopyroxene
l150oC
and 15kbar.
and
in
T-Ⅹ
the
of
were
spinel, and quartz
Orthopyroxene
The
increases
product
show
the
capsules
results,
results
Fe-free
the
Spinels
run
at
solubility
1977), the alumina
than
and
Graphite
In
丘eld
phase
temperature
in
starting
method.
like-, elongated
needle
experimental
in Fig. 1.
solubility.
lOkbar
and at
given
The
Hariya
fo乞--10
Orthopyroxene,
orthopyroxene＋spinel＋quartz
of the join. The
solubility
alumina
a
by
the
were
for
correction
was唱nOred.
for
atm･
di任raction
coexisting
T-Ⅹ
alumina
of
1200oC
at
results
a
1.
X-ray
in
as
orthopyroxene
The
The
results
and pressures
(Fig. 1). The
present
temperature.
1
products
temperatures
diagrams
A1203
of
the
on
studied,
phase丘eld
Table
20FLm
to
up
transmittlng
method.
given
optlCally
pressure
described
prepared
Experimental
The
glass-
±10oC.
method
were
experimental
with
Pyrex
thermocouple
lOOOoC,
at
apparatus
as
as
of Geology
length.
in
used
of olivine-spinel-cristobalite.
containers.
X-ray
piston-cylinder
5.00cm
estimated
mixtures
crystallized
composed
the
Pt-PtRh13
of
by
crystalline
were
mixtures
which
was
Department
the
at
and
cells
e.m.f.
was
using
diameter
accuracy
quarヒz.
out
carried
pressure
Under
a
methods
University,
Hokkaido
volume
working
were
experiments
Mineralogy,
in
experimentally
the P-T
conditions
is determined
Mg/(Mg＋Fe2＋)-0.754=
with
temperature
ARIMA
this
study
proportion
of
the
startlng
contain
Fe
data
of the
lines at
diffraction
as
High
Aluminous
Table
Corpposition
Startlng
1.
of
(oC)
%)
Vt.
Experimental
Temp.
Materials
(A1203
Orthopyroxene
2. 5
〝
〝
5. 0
Press.
Time
(hrs)
Results
950
10
51
Opx,
Sp,
Qt
1 000
1 000
10
50
Opx,
Sp,
Qt
15
15
65
5
65
2
Opx
Opx
10
10
73
109
44
3
5
Opx,
Opx
6
Opx
Opx,
only
48
Sp,
Qt
Sp,
Qt
1 000
1 050
1 075
〝
results.
(kbar)
1 050
〝
33
only
only
Sp,
〝
1 000
10
15
〝
1 025
15
41 5
Opx,
〝
1 050
15
48
Opx
only
1 100
1 150
48 7
18
26
Opx,
Opx
Opx,
only
Op∑
only
〝
7. 5
Qt
only
〝
1 100
10
10
15
〝
1 150
15
45
10. 0
1 000
1 100
10
10
48
0px,
Sp,
Qt
24.5
1 150
10
42
0px,
0px,
Sp,
Sp,
Qt
1 200
1 100
10
15
27. 5
47.5
1 150
15
43
〝
〝
〝
〝
〝
〝
Sp-spinet,
Opx-orthopyroxene,
Temp･
1
Sp,
Sp,
0px
only
0px,
0px
only
Sp,
Qt
Qt
Qt
Qt
Qt-quartz.
1
0kbQr
5kbcLr
(oc)
′
′
′
●
1200
′
′
′
′
′
′
′
′
Opx
●
●
■′
Opx
′
∫
′
1100
′
′
′
●
0
1000
●
0px◆Sp◆Oz
0
0
0
10
5
0
Opx･Sp●Qz
900
5
A1203
Fig.
1.
T-Ⅹ
Solid
kbar.
of
alumina
(Arima
in
sections
15
and
in
and
a
part
broken
orthopyroxene
Onuma,
1977).
10
AL203
Wt･%一･
in
---
join (Mgo.754Feo.246)SiO3-Al芝03
of the
lines
Wt･%
indicate
the
respectively
present
Opx-orthopyroxene,
system
the
and
Sp-spinel,
at
10
and
limit
solubility
Fe-free
systen1
Qz-quartz.
34
lower
relatively
in
than
angles
those
M.
ARIMA
for
pure
splnel,
a
suggesting
of Fe
presence
its structure.
Cell
The
丘eld
parameters
of
unit cell paremeters
determined
by using
were
of
orthopyroxenes
following
the
in
occurlng
orthopyroxenes
di任raction
as
an
external
by
the
calculated
Fig. 2 shows
the
with
The
study
the
cell
cell
parameters
that
found
for
cell
edges
a
a
show
pyroxenes.
in the
variation
Sakurai
b,
a,
The
with
decrease
cell
the
contrary,
compositional
of
Silicon
1964 ; Arima
V
edge
studied.
of the
alumina
c
does
not
Comparing
the
of
of 0.754= is identical
1977).
and Onuma,
in
orthopyroxene
in the
content
any
show
the
5.22
18.25
5.20
51.8
18.20
v(Å3)
b(A)
8.88
8
50
8,84
840
8.80
830
8.76
5
10
A1203
Fig.2.
The
content
cell
in the
edges
5
10
AI203
Wt..I.
a,
synthesized
---･
b,
and
c,
and
orthopyroxenes.
cell
volume
l′ agalnSt
Wt.%一-
the
this
ortho-
systematic
present
c(A)
1
ortho-
incorporation
a(A)
i I
was
were
parameters
alumina
Mg/(Mg＋Fe2＋)
volume
cell
range
effect
increaslng
with
(060), (10, 31),
V
cell volume
Boyd,
(Skinner and
cell
phase
(1968).
the
and
c,
in orthopyroxene
the
The
measurement.
by
join.
enstatite
and b and
the
the
studied
systematic
On
edges
in the
synthesized
pyroxenes
on
for
standard
UNICS
program
slngle
(630).
(250), (541), (640), (621), (631), (241), (820), (721), (531), and
used
the
lines:
alumina
results
High
with
Arima
those
sten
and
in
Seifert,
1981), the
line
a
along
compositional
aluminous
and
and
and
with
that
b
for
(Grammenopoulou,
in
of the
the
present
variation
Anner-
different
with
cell
of
1964;
orthopyroxenes
orthopyroxenes
non-linear
splitting
Fe2＋ in
as
The
(1968)･
Synthesized
have
which
(QS) of 2.1 mm/sec,
The
former
MI
a
site
result
done
Was
A1203
%
doublets
respectively.
letter
Hafner
two
of
quadropole
4･07mm/see
the
parameter
measurement
lOwt.
with
consists
and
Boyd,
identical
studied (Fig. 2) is almost
the FeO-free
system
(Skinner and
spectroscopIC
orthopyroxene
spectrum
and
(Skinner
volume
with
I∋oyd,
along
found
that
1964;
for
Arima
1977).
M6ssbauer
the
in
enstatites
Onuma,
cell
(Fig. 3). The
range
35･
Mg/(Mg＋Fe2＋)-0.5
compatible
ratios
Orthopyroxene
Mg/(Mg＋Fe2＋)-1.0
with
1977) and
Mg/(Mg＋Fe2＋)
the
systems
Onuma,
and
plotts
the
Aluminous
in
the
15kbar.
The
and
of 1.01mm/sec
Fe2＋
as
assigned
structure
90wt.
than
more
on
shift (CS) of 1.02 mm/sec
orthopyroxene
that
suggests
was
temperature
room
l150oC
at
chemical
and CS
doublet
a
at
%
8･94｢
8.90
8.86
0.5(Mg/Mg＋Fe)
c言
ヽ-′
8.82
.上】
(MgノMg＋Fe)
o.754
8.78
⊂1
8.74
1.0
(Mg/Mg十Fe)
8.70
0
0.1
0.2
A]
Fig.
3.
The
cell
orthopyroxenes
ious
0.3
atoms
edge
per
b
six
ratios｡
0.5
in
0.6
0.7
oxygens
the
against
synthesized
Mg/(Mg＋Fe2＋)
0.4
the
alumina
systems
content
with
ir1
var･
a
after
of
QS
and
in
Fe2＋
M2
of
site
Virgo
present
36
in
M.
M2
a
ferric
a
at
site
iron
The
temperature.
room
is probably
which
ARIMA
data
in
negligible
no
shows
the
slgn
a
Of
presence
of
studied.
orthopyroxenes
Discussion
The
Mg-Tschermak's
important
hypothetical
1973).
The
studied
are
Al
in
as
in the
parameters
results
site
lead
w.hich
as
considered
(cf. Wood
and
to
in
an
Banno,
join
the
along
orthopyroxenes
by Al
of Mg
of replacement
tetrahedral
a
been
component
end-member
of cell
interpreted
Si by
site and
pyroxene
variations
has
(MgA12SiO6)
component
a
octahedral
Mg-Tschmak's
the
com-
ponent.
The
present
(ss) breaks
This
the
to
breakdown
indicate
results
experimental
down
assemblage
of
can
be written
reaction
that
the
aluminous
orthopyroxene
(ss)＋spinel (ss)＋quartz.
orthopyroxene
as:
MgA12SiO6-MgA1204＋SiO2.
Opx(ss)
As
is
spinel
bearing
an
Fe-free
to
in
pressure
and
a
the
as
system
range
that
used
this
SPinel-
down
(ss) breaks
(ss)＋quartz
in
a
MgO-FeO-Al203-SiO2.
orthopyroxene
(ss)＋sapphirine
orthopyroxene
1977), suggesting
Qt
join (Mg..754Fe..246)SiO3-A1203,
the
should
considered
MgSiO3-A1203,
aluminous
system
assemblage
perature
belong
Sp(ss)
be
assemblage
In the
to
longer
no
(1)
the
at
(Arima
study
tem-
same
Onuma,
and
:
reaction
2MgA12SiO6-Mg2Al4SiOIO＋SiO2.
Opx(ss)
In the
The
present
results
a
narrow
and
that
has
relation
Mg-Fe-AトSi-0
Hermans
product.
longer
no
in this study.
used
sapphirine
has
in
stable
Similar
and
tem-
stability
spinel
in
the
fo乞 fugacities･
rel-ations
between
orthopyroxene,
effect of Fe2＋
be
can
ratio
the
of
higher
and
incorporation
alumina
reducing
increase
of
FeSiO3
leads
an
increase
to
is
sapphirine
(1986) for
partitionlng
it
et al., 1976;
ential
that
high
relatively
run
any
Sapphirine
solid solution
Fe-sapphirine
in the
composition
that
as
in
occur
System
and
Hensen
not
sap-
the
the
estimated
possible
In the granulite
facies metamorphic
rocks,
is lower
than
that
orthopyroxene
of coexisting
on
of Al in ortbopyroxene.
Mg/(Mg＋Fe2十)
sapphirine
at
Mg-Fe
the
spinel,
phirine,
and
incorporation
such
by
suggested
system
Considering
studied,
range
Qt
does
a
toward
composition
been
Sa(ss)
sapphirine
Fe-bearlng
the
range
pressure
Fe2十-enriched
the
in
compositional
perature
a
experiments,
indicate
(2)
than
that
of
Caporuscio
of Fe
coexisting
Morse,
and
in spinel, Eq.
content
component
of alumina
(1)
of coexisting
in orthopyroxene
content
in
spinel
1978;
tends
(Nixon
Grew,
to
be
1980).
displaced
On
orthopyroxene.
coexisting
orthopyroxene
the
sapphirine
as
et
al., 1973;
With
to
prefer-
the
right,
contrary,
and
an
quartz
Fe乞＋ preferentially
High
Aluminous
Orthopyroxene
37
A 1203
/
/
/
十Qt
Sass
Spss
/
/
Opxss
M90
Fig.
4.
FeO
Schematic
between
the
indicates
atically
in
the
shows
under
the
content
in
In the
(ss), and
and
orthopyroxene
and quartz.
facies metamorphic
(800-1000oC)
temperatures
Natural
been
described
land,
Antarctica
and
from
ities･
Based
McLellan
OAO
(Ellis
been
on
(1985)
in
was
of
in relatively
1985)
has
et
and
conditions
splnel-quartz
4 schem-
orthopyroxene
MgO-FeO-Al208-SiO望
this
The
study.
of
highest
the
value
alumina
it coexists
when
an
reported
the
equilibrium
1980;
are
by
with
and
in
the
compositional
with
Onuma
same
The
more
Enderby
1984),
Tracy
and
orthopyroxene＋sapphirine＋
harmonious
Arima
sapphirine-quartz
1978;
Mg/(Mg＋Fe2＋)
Those
are
stable
spineトquartz
under
different
of
starting
compositions･
replaces
have
Matsueda,
and
Morse,
from
the
rocks
Peekskill,
New
York,
on
spinel
rocks
high
1980 ; Grew,
Mg-enriched
quartz･
with
and
aluminous
studies
only
(cf. Ellis,
pressure
are
extremely
under
Motoyoshi
(Caporuscio
assemblage
that
ortho_
orthopyroxene＋spinel＋quartz
from the Napier
rocks
complex,
Grew,
in relatively
aluminous
of
formed
partial
aluminous
petrologlCal
suggested
been
water
York
occurrences
orthopyroxene＋spinel＋quartz
have
to
all, 1980;
New
whereas
rocks,
Fe-enriched
sapphirineand
splnel-bearlng
in this
done
those
study and
quartz
at
aluminous
lower
and
occurrences
Peekskill,
quartz
between
system
conditions
Fig.
Sapphirine.
splnel
ganulite
McLellan,
in the
spinel
line
broken
experiments.
coexistlng
reach
and
A
present
quartz
would
relations
(ss),
relationships
pressure
pyroxene＋sapphirine＋quartz
and
rare
have
been
and
considered
1980)･
the
compositional
(ss), spinel
the
in
than
rather
possible
temperature
sapphirne,
with
join studied
the
compositional
MgO-FeO-A1203-SiO2.
system
orthopyroxene
(ss), sapphirine
showing
(ss), sappbirine
orthopyroxene
(ss) in
incorporates
diagram
Tracy
ratio
Fe2十-enriched
and
study
results
sapphirine_
temperature
present
than
between
the experimental
where
and
less
relations
(1977),
local-
same
suggests
rocks.
pressure
that
38
M.
discussed
As
oxidation
be
might
in
splnel
of alumina
that
in orthopyroxene.
As
and
be
would
orthopyroxenes･
phirine＋quartz
restricted
be
partly
Leong
to
A1203
by
the
oxidation
of
(1978)
conditions
as
metamorphic
state
oxidation
aluinous
well
orthopyroxenes
grade
high
relatively
relatively
in
high
the
with
solubility
Arima
MgSi-Fe3十Al
COntentS
in
involving
in the
role
substitution
occurrences
rocks
of
orthopyroxene＋sap-
highMg/(Mg＋Fe乏＋)
ratios
of high
consequences
(Seifert, 1974;
the
silicate
of sapphirine
reactions
high
relatively
spinel-quartz
rare
to
important
high
attributed
Moreover,
would
or
partly
an
in
ratios
experimentally
under
Extremely
Sapphirine-quartz
oxidation
to
related
relations
The
play
by
chemistry
stability
demonstrated
alumina
MgSi-AIAl.
coexistlng
also
(1981),
incorporates
the
rocks.
would
of
for
quartz-bearing
mineral
Mg/(Mg＋Fe2＋)
of
processes
Seifert
in
changes
increases
phases
Annersten
rocks
including
the
orthopyroxene
as
(1986),
important
Fe-oxide
silicate and
and
Hensen
reactions,
phases,
and
by
ARIMA
during
oxidation
conditions
metamorphism
1972; Caporuscio
Morse,
1978).
and
Moore,
and
Acknowledgements
l would
like
Yu
express
through
encouragement
and
to
Hariya
for
assistance
I
discussion
pressure
Emeritus
to
gratitude
this study.
helpful
high
on
my
am
indebted
also
Mr.
to
and
Professor
Kenzo
Drs.
to
Shoichi
Yagi
Kosuke
for
Onu皿a
for technical
Terada
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