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The garnet-clinopyroxene Fe-Mg

geothermometer - a reinterpretation of
existing experimental data

Article in Contributions to Mineralogy and Petrology May 1988

DOI: 10.1007/BF00399364

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Contrib Mineral Petrol (1988) 99: 44-48
The garnet-clinopyroxene F e - M g geothermometer
- a reinterpretation of existing experimental data
Erling J. Krogh
Institute of Biology and Geology, University of Tromso, N-9000 Tromso, Norway
Abstract. Experimental data on the partitioning of Fe 2 +
and Mg between garnet and clinopyroxene (R~heim and
Green 1974; Mori and Green 1978; Ellis and Green 1979)
have been used to construct a new expression for the garnet-
clinopyroxene geothermometer, including a curvilinear rela-
tionship between lnKd and Xc,(ga):
T(~ = ( ( - 6173 (Xc,) 2 + 6731 Xc, + 1879
+ 10 P (kb))/(ln Kd+ 1.393)) ' 273
Application of this geothermometer to a suite of samples
of eclogites and associated omphacite-garnet-bearing gneis-
ses from the uppermost allochthon within the North Nor-
wegian Caledonides shows that the calculated temperatures
do not vary with rather great variations in the mg number
of the garnet (0.17-0.54) and Na content of the clinopyrox-
erie (0.11-0.44). Temperatures below 900 ~ C calculated us-
ing the present equation are somewhat lower than those
obtained by the method of Powell (1985), the difference
being larger for lower temperatures and lower values of
Xc~.
Introduction
The distribution of Fe z + and Mg between coexisting garnet
and clinopyroxene is expressed by the exchange reaction:
1/3Mg3A12Si3011 + CaFeSizO6
Pyr Hed
= 1/3FeaA12SiaO12 + CaMgSi206
Alm Di
with the distribution coefficient given as:
Kd= (Fe2 +/Mg)g,/(Fe 2 +/Mg)Cpx= f ( T , P, X)
where T is the temperature in K, P the pressure and X
the chemical composition of the two minerals. The relation-
ships between Kd and each of these parameters are given
by the general equations:
l n K d = A/T+ B; (P, X) . . . . t
in Kd(P') = In Kd(P) + C/T* (P-- P'); (T, X) .... t
lnKd=f(X); (T, P) .... t
A and B are constants
c = A v/R
A V= volume change for reaction (1)
R = gas constant
32 in Eq. (5) will essentially be Xc, = Ca/(Ca + Mn + Fe + Mg) in
garnet.
Contributions to
Mineralogy and
Petrology
9 Springer-Verlag1988
Based on the experimental data from Rfiheim and Green
(1974a, b), Mori and Green (1978) and Ellis and Green
(1979), the system can now be calibrated.
Methods
Ellis and Green (1979) used the experimental data at
1200 ~ C/30 kbar to establish a rectilinear In Kd=f(Xc. ) rela-
tionship expressed as:
lnKd= 2.1066 Xca + 0.3753 (6)
Powell (1985) gave a slightly different slope for this relation-
ship. Hoinkes (1986) showed a curvilinear relationship be-
tween In Kd and Xc. for the system garnet/biotite:
l n K d = -- 5.906 (Xca) z + 2.978 Xc,-- 1.7500 (7)
The experimental data from Rfiheim and Green (1974a,
b). Morri and Green (1978) and Ellis and Green (1979)
at 1100 and 1200 ~ C (Table 1) also indicate a curvilinear
relationship between lnKd and Xc~ for the garnet/clinopy-
roxene system (Fig. 1), and quadratic regression equations
for these two datasets are given as:
In Kd(ll00) = -- 5.212 (Xc.) 2 + 5.287 Xc, + 0.121 (8)
and
In Kd(1200) = - 3.464 (Xca) z + 4.173 Xc~ + 0.134 (9)
(1) An averaged curve for T = 1150 ~ C gives:
lnKd(l150) = - 4.338 (Xca)2 + 4.730 Xc~ + 0.127 (10)
The following procedure for the calibration of the garnet/
clinopyroxene geothermometer is adopted:
1) For any given J(Ca in the experimental data at any tem-
(2) perature, the corresponding lnKd at 1150 ~ C can be calcu-
lated according to Eq. (10).
2) From the experimental lnKd(T) at temperature T and
the calculated lnKd(ll50), both for the same Xc,, a lnKd
vs. lIT relationship can be calculated:
In Kd= ((ln Kd(7) -- In Kd(l 150))/(1/T-- 1/ 1423)) 9 1/ T + B(I 1)
(3)
(4) 3) By inserting the correction factors for Xc, from Eq. (10)
(5) into Eq. (11), a general expression for lnKd is obtained:
In Kd= (-- 6173 (Xca) 2 "1- 6731 Xc, + A')/T+ B (12)
ln Kd for a particular datapoint at a certain temperature
T can now be calculated at any JQa-
The calculation procedure as described above has been
done for the experimental data at 600, 700, 750, 800, 900,
Table 1. Data used in the calibration of the garnet/clinopyroxene geothermometer

Run no. Xc~ lnKd lnKd(0.20) T e ( ~ C) T c ( ~ C) z~T

4549 0,355 2,934 2.347 600 603 3

4517 0,299 2,351 1.979 700 699 - 1
T-110 0,220 1.936 1.855 750 737 - 13
T-81 0.324 2.255* 1.831 1.787 750 744 -6
T-126 0.332 2.119" 1.675 750 790 40
4465 0.244 1.872 1.708 800 785 - 15
4422 0.181 1.504 1.575 900 830 --70
T-88 0.192 1.452 1.481 900 867 --33
T-72 0.230 1.579 1.475 900 871 --29
T-96 0.235 1.456 1.335 1.422 900 927 27
T-72 0.273 1.587 1.350 900 920 20
T-72 0.297 1.683 1.380 900 908 8
T-96 0.328 1.739 1.360 900 916 16
M&G 0.15 0.936 1.051 I000 1036 36
M&G 0.15 0.996 1.176 1000 1004 4
4242 0.154 1.099 1.264 1000 959 -41
M&G 0.18 1.106 1.175 1.180 1000 1004 4
4233 0.191 1.194 1.225 1000 979 -21
4558 0.200 1.194 1.194 1000 994 -6
4243 0.235 1.224 1.113 1000 1034 34
M&G 0.15 0.860 1.032 1050 1081 31
M&G 0.155 0.953 1.108 1.074 1050 1037 - 13
M&G 0.18 1.017 1.083 1050 1051 1
4369 0.113 0.642 1100 1133 33
4240 0.151 0.766** 1100 1142 42
4332 0.161 0.838 ** 1100 1118 18
4368 0.185 0.993 1100 1074 --26
4239 0.194 0.956 1100 1112 12
4587 0,203 0.956 1100 1128 28
4725 0.205 0,993 1100 1110 10
4769 0,246 1.090'** 0.968**** 1100 1121 21
4267 0,248 1.121"** 1100 1107 7
4774 0.263 1.103"* 1100 1138 38
4766 0.266 1,121 *** 1100 1132 32
4739 0,268 1,103"* 1100 1145 45
R&G 0,440 1,398 1100 1141 41
T-43A 0.472 1.460 1100 1122 22
T-52 0,113 0,548 1200 1201 1
M&G 0,15 0,681 1200 1197 --3
4367 0,153 0.742 1200 1162 --38
T-26 0,158 0.673 1200 1222 22
T-53 0,194 0.878 1200 1159 --41
4268 0.196 0.788 1200 1222 22
4724 0,203 0.765 1200 1252 48
T-47 0.207 0,737 0,831"**** 1200 1280 80
T-47 0,207 0.793 1200 1240 40
T-53 0.207 0.982 1200 1120 -80
T-47 0,227 0,833 1200 1249 49
T-52 0,245 0.952 1200 1201 1
T-53 0.288 1,073 1200 1189 11
T-26 0.308 1.109 1200 1192 --8
T-52 0,385 1.233 1200 1195 --5
T-26 0.437 1.292 1200 1195 --5
T-52 0.454 1.308 1200 1194 --6
M&G 0.15 0,596 0.746 0.766 1250 1260 10
M&G 0.16 0.668 0.786 1250 1230 --20
4730 0.145 0,531 0.691 1300 1299 -- 1
T-27 0.170 0,647 0.732 1300 1269 --31
4727 0.201 0.588 0.588 0.696 1300 1384 84
T-27 0,228 0.842 0.769 1300 1245 --55
T-27 0,311 0.896 0.644 1300 1333 33
T-27 0.459 1.191 0.753 1300 1263 --37

* Minimum lnKd values

** and *** Experiments at 20 and 40 kbars, respectively, normalised to a pressure of 30 kbars according to Eq. (4), using C = - 1 0
**** and ***** Values calculated according to Eqs. (8) and (9), respectively
M&G - Mori & Green 1978 T-series - Ellis & Green 1979
R&G - Rg~heim & Green 1974b All other data from Rfiheim & Green 1974a
46

1.6 1000, 1050, 1250 and 1300 ~ C/30 kbar, and Xca is arbitrarily
/X 1 1 0 0 C / 3 0 kbar fixed at a value o f 0.20 (Table I). Where there is m o r e
1.4- [] 1 2 0 0 C / 3 0 k b a r / , / , - ~ than one d a t a p o i n t at one temperature, the calculated
lnKd(0.20) values are averaged, lnKd(0.20) values for 1100
a n d 1200~ C are calculated according to Eqs. (8) and (9),
1.2 respectively. The averaged lnKd(0.20) values are plotted
against 1/T (Fig. 2), and the linear regression curve (at
1- /k 30 kbar) is given by the equation:
l n K d = 3 2 7 8 / T - 1.393 (r 2 = 0.9993) (13)
.8 i
Inserting the correction factors for XCa, and a pressure cor-
rection factor A V/R= - 10 (Powell 1985) gives the general
.6 geothermometer equation:
T(~ = ((-- 6173 (Xca) 2 -t- 6731 )(ca + 1879 + 10 P)/(ln Kd +
.4 I I ) I I I I 1.393))--273 (14)
.1 .2 .3 .4 .5
XCa In Table 1 calculated temperatures (Te) for all the d a t a
Fig. 1. ,e~Ca VS. lnKd for experimental data at lt00 and 1200 ~ C used in the present calibration are given together with the
and 30 kbar, showing curvilinear relationships deviation (A T= To--Te) from the experimental tempera-
ture (Te).

2.4 Application
2.2
In Kd(0.2) = 3278T - 1.393 " / ~ 0 0
- The present geothermometer has been used to calculate
2.0- r 2 = 0.9993 _/__
9 700 equilibration temperatures for a suite o f 17 samples o f eclo-
gites a n d associated high pressure (omphacite-beafing)
/ gneisses from the T r o m s o n a p p e complex within the north-
1.8- / / ~ 0 9 750
0 ern Scandinavian Caledonides ( K r o g h E J, Andresen A,
d 1.6- Bryhni I, Kristensen SE (1988) T e c t o n o m e t a m o r p h i c evolu-
"13 tion o f the eclogite-bearing u p p e r m o s t allochthon, N o r t h
~e 1 . 4 - m 900 N o r w e g i a n Caledonides. Submitted to J M e t a m o r p h i c
t-

1.2- Geol), showing wide ranges in the compositions o f b o t h

. / 9 1000 garnets and clinopyroxenes (Table 2). Xca varies between
m'1050
1.0 - /m
./
1100
0.15 a n d 0.44, and the mg n u m b e r o f the garnets lies in
the interval 0.17-0.54. Na~P2x in the clinopyroxenes are in
.8 1200
, 9 1250 the range 0.11-0.44. The calculated temperatures range
/1113001 I I I I from 690 to 790 ~ C, with a mean value o f 731 ~ C. The
6 7 8 9 10 11 12 calibration o f Powell (1985) gives b o t h a larger spread
I/T * 104 (708-832 ~ C) and overall higher temperatures. A t Xca = 0.15
Fig. 2. 1/T vs. In Kd normalised to Xca = 0.20 and P = 30 kbar, based the difference between the two calibrations is > 50 ~ C, de-
on data from Table 1 creasing to 1 2 ~ at Xca=0.31, and then increases again

Table 2. Chemical compositions of garnets and clinopyroxenes, Kd values and calculated temperatures for a suite of samples of eclogitic
rocks from the Tromso nappe complex, northern Scandinavian Caledonides. TK - present calibration; Tp - Powell (i 985)

Sample Xca mg number Na~r~ Kd TK(~ C) Te( ~ C)

82015 0.31 0.46 0.39 7.91 744 756

82016 0.23 0.51 0.37 6.43 726 745
82017 0.t5 0.43 0.44 4.48 729 782
T-8 0.22 0.55 0.39 6.55 708 732
T-11 0.26 0.26 0.40 6.09 777 788
T-t 3 0.25 0.50 0.23 7.00 723 739
T-20 0.40 0.25 0.39 9.43 753 782
T-24 0.29 0.23 0.36 8.17 718 731
T-26 0.32 0.30 0.36 9.58 699 714
1A 0.44 0.44 0.12 8.81 790 832
1758 0.17 0.54 0.11 4.85 737 777
580 0.26 0.53 0.20 6.88 739 752
82006 0.26 0.21 0.33 8.20 691 708
82008A 0.27 0.27 0.35 7.85 713 727
82008B 0.25 0.32 0.30 6.25 758 771
82010 0.28 0.37 0.30 7.55 690 710
T-17 0.26 0.17 0.44 6.96 738 751

800 I I I I
r
750
700
650 ~ ~ ~ ~
.2 .3 .4 .5
[ M g / ( M g + Fe)] go
to 40 ~ C at Xc~ = 0.44. Plots of the calculated temperatures
(T~ in Table 2) vs. the mg number of garnet (Fig. 3 a) and
N~Cpx
~M2
(Fig. 3b), respectively, show no systematic correla-
tion. This suggests that these parameters have only minor
effect on the Kd value, which is in conflict to the experimen-
tal data of (Pattison and Newton 1987). Their data do sug-
gest that the Kd value is dependent on the mg number
of the garnet.
Discussion
This study shows that the major compositional effect on
the partitioning of Fe 2 + and Mg between garnet and clino-
pyroxene is the grossular content of the garnet. In the range
Xc~ = 0.10-0.50 this effect is better approximated by a qua-
dratic rather than a rectilinear equation as proposed by
e.g. Ellis and Green (1979). Dempsey (1980) showed that
low-Ca garnet (PY9oGrlo) have the space group I213 rather
than Ia3d, and suggested a structural change in garnet
caused by cation ordering in the 8-coordinated sites. The
substitution of the larger Ca 2 + cation into the almandine
(or pyrope) structure will lead to an expansion of the 8-
coordination sites occupied by Ca, and a possible distortion
of the structure, resulting in the local generation of non-
equivalent 8-coordinate sites, and the ordering of Ca and
Fe (Mg) atoms between these (Cressey 1979). The conse-
quence of this distortion and expansion of the structure
by Ca replacing Fe(Mg) is that as the structure is 'opened
up' the smaller cations (Fe 2+, Mg 2 may begin to exercise
random occupancy of possible sub-sites within the ex-
panded 8-coordinate sites (Cressey 1981). At a certain value
of Xc~ all of the Fe (Mg) atoms will be randomly distributed
on these sub-sites. No such sub-sites are expected in pure
almandine or pyrope garnets. Compared to Fe z +, Mg are
expected to more readily enter the sub-site disorder for a
given expansion of the garnet structure, because of its
smaller size (Cressey 1981). This may again result in an
enrichment of Mg relative to Fe 2 in garnets with XCa be-
tween 0 and the value where all the Fe and Mg atoms
are randomly distributed on the sub-sites. As a conse-
quence, this will affect the distribution of Fe / + and Mg 2+
between garnet and a coexisting FeMg phase in this interval
of Xc, towards lower Kd-values. The curvilinear relation-
ship between lnKd and Xc, as shown in Fig. 1 clearly dem-
onstrates that this assumption is valid. Further, at still lower
values of Xca , this curve is expected to pass through a
minimum value for lnKd, with increasing values again to-
wards Xc, = 0. The exact mathematical expression for this
curve is thus not even described by a quadratic equation,
47
I
.k
-k "A"
~r
Fig. 3. a mg number for garnet and b
,k "/~" Na~r~ in clinopyroxene plotted vs.
calculated temperatures for eclogitic
rocks from the Tromso nappe
~ i complex
.2 .3 .4
NaMPX
but as an equation of higher degrees. However, as an ap-
proximation the quadratic expression is satisfactory for the
interval Xca=0.10-0.50. The critical Xc,-value for a ran-
dom distribution of all Fe and Mg atoms on the subsites
in garnet appears from the data at 1200 ~ C/30 kbar to be
around 0.25-0.30.
Even though most of the current available data on coex-
isting garnet and clinopyroxene are used in the present cali-
bration of the system, this geothermometer is still hampered
with several major problems:
1) There are very few experimental data at lower (crustal)
temperatures. However, Schliestedt (1986) used a prelimi-
nary version of the present geothermometer on low temper-
ature eclogites and blueschists from Sifnos, and concluded
that the calculated temperatures were in accordance with
those estimated by other methods (calcite-dolomite solvus,
Schliestedt 1980; and oxygen isotope fractionations be-
tween different mineral pairs, Matthews and Schliestedt
1984). The Ellis and Green (1979) geothermometer and the
revised version of Powell (1985) gives too high equilibriurn
temperatures by ca. 50 and 30 ~ C, respectively, for these
rocks.
2) The relationships between lnKd and Xca is not fully es-
tablished yet, especially in the low Xca region. This will
be critical for estimation of temperatures for garnet perido-
tites, 'orthopyroxene eclogites' and other rocks containing
low-Ca garnets.
3) The problem of the determination of ferrous/ferric iron
in the clinopyroxenes is not solved. If Fe z+ and Fe 3 are
not analysed separately, various calculation methods are
available (e.g. Cawthorne and Collerson 1974, Neumann
1976). These calculations can, however, not take care of
problems such as nonstoichiometry in clinopyroxene
(Wood and Henderson 1978), and the possible presence
of submicroscopic intergrowth/exsolution of low-SiO2
phases (e.g. amphibole) in the clinopyroxene (Veblen and
Buseck 1981), and they are further sensitive to analytical
errors, and may be catastrophical for clinopyroxenes which
are low in Fetot, as those from garnet ultrabasites.
4) Any possible effects of chemical variations in clinopyrox-
ene on the Kd value are not included in the present calibra-
tion. Such effects could be caused by variations in the ja-
deite content, especially at Xja > 0.6 (Koons 1984; Heinrich
1986). However, Xja will in most cases be lower than 0.6,
and as shown by Koons (1984), Heinrich (1986) and also
in Fig., 3b of this paper, the Kd values do not seem to
vary with Xja in the range 0.10-0.6. If (Na + Ca) cpx~ 1, this
certainly will affect the F e - M g distribution in the system.
This problem is probably negligible at ordinary crustal tem-
peratures, but will increase with increasing temperatures.
48
5) The dependence o f Kd on the mg n u m b e r o f the garnet
as reported by Rfiheim and Green (1974a) and Pattison
and N e w t o n (1987) is n o t confirmed by the d a t a from the
eclogitic rocks from the T r o m s o n a p p e complex (Table 2;
Fig. 3 a), at least in the range M g / ( M g + F e ) = 0.17-0.55.
Acknowledgements. I will like to thank an anonymous reviewer
for valuable comments which certainly have improved the manu-
script.
References
Cawthorn RG, Collerson KD (1974) The recalculation of pyroxene
end-member parameters and the estimation of ferrous and ferric
iron content from electron microprobe analyses. Am Mineral
59:1203-1208
Cressey G (1979) Mixing properties of aluminosilicate garnets. Ph
D Thesis, Manchester Univ
Cressey G (1981) Entropies and enthalpies of aluminosilicate gar-
nets. Contrib Mineral Petrol 76: 413-419
Dempsey MJ (1980) Evidence for structural changes in garnet
caused by calcium substitution. Contrib Mineral Petrol
71 : 281-282
Ellis DJ, Green DH (1979) An experimental study of the effect
of Ca upon garnet-clinopyroxene F e - Mg exchange equilibria.
Contrib Mineral Petrol 71 : 13-22
Heinrich CA (1986) Eclogite facies regional metamorphism of hy-
drous marie rocks in the Central Alpine Adula Nappe. J Petro-
logy 27:t23-154
Hoinkes G (1986) Effect of grossular-content in garnet on the parti-
tioning of Fe and Mg between garnet and biotite. Contrib Min-
eral Petrol 92: 393-399
Koons PO (1984) Implications to garnet-clinopyroxene geother-
mometry of non-ideal solid solution in jadeitic pyroxenes. Con-
trib Mineral Petrol 88:340-347
Matthews A, Schliestedt M (1984) Evolution of the blueschist and
greenschist facies rocks of Sifnos, Cyclades, Greece. A stable
View publication stats
isotope study of subduction-related metamorphism. Contrib
Mineral Petrol 88:150-163
Mori T, Green DH (1978) Laboratory duplication of phase equilib-
ria observed in natural garnet lherzolites. J Geol 86:87-97
Neumann ER (1976) Two refinements for the calculation of struc-
tural formulae for pyroxenes and amphiboles. Nor Geol
Tidsskr 56 : 1-6
Pattison DRM, Newton RC (1987) Garnet-clinopyroxene KD(Fe-
Mg) : Variations due to Xc, Grt
and pressure (abstract) EOS Trans
AGU 68:46l
Powell R (1985) Regression diagnostics and robust regression in
geothermometer/geobarometer calibration: the garnet-clinopy-
roxene geothermometer revisited. J Metamorphic Geol
3 : 231-243
RSheim A, Green DH (1974a) Experimental determination of the
temperature and pressure dependence of the Fe-- Mg partition
coefficient for coexisting clinopyroxene and garnet. Contrib
Mineral Petrol 48:179-203
R~theim A, Green DH (1974b) Experimental petrology of lunar
highland basalt composition and applications to models for
the lunar interior. J Geol 82:607-622
Schliestedt M (1980) Phasengleichgewichte in Hochdruck-Ge-
steinen von Sifnos, Griechenland. Dr rer nat thesis, Univ
Braunschweig, 142 pp
Schliestedt M (1986) Eclogite-blueschist relationships as evidenced
by mineral equilibria in the high-pressure metabasic rocks of
Sifnos (Cycladie Islands), Greece. J Petrology 27:1437-1459
Veblen DR, Buseck PR (1981) Hydrous pyriboles and sheet sili-
cates in pyroxenes and uralites: Intergrowth mierostructures
and reaction mechanisms. Am Mineral 66:1107-1134
Wood BJ, Henderson CMB (1978) Composition and unit cell pa-
rameters of synthetic non-stoichiometric Tschermakitic clino-
pyroxenes. Am Mineral 63:66-72
Received June 22, 1987 / Accepted February 2, 1988
Editorial responsibility: J Hoers