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Clinopyroxene–melt trace element partitioning and the development of a predictive model for HFSE and Sc
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Journal Article
Clinopyroxene–melt trace element partitioning and the development of a predictive model for HFSE and Sc
2011
Overview
Clinopyroxene–melt trace element partitioning experiments were carried out in the system Na
2
O–CaO–MgO–Al
2
O
3
–SiO
2
at pressures of 1, 2.3 and 3 GPa and temperatures of 1508 to 1811 K, to investigate the effects of temperature (
T
), pressure (
P
) and composition (
X
) on partition coefficients. Of particular interest were elements entering the octahedral M1-site. Ion probe analyses of run products produced crystal–melt partition coefficients (
D
) for 16 elements (Na, Ca, Al, Cl, Sc, Ti, Fe, Zr, In, La, Ce, Nd, Sm, Ho, Yb and Hf). With the exception of
D
Na
, partition coefficients for all elements studied decrease with increased
P
and
T
, despite the concomitant increase in the Al content of the T-site. Fitting partition coefficients for isovalent series of cations to the elastic strain model of Blundy and Wood (
1994
) produced values for the site radius (
r
0
), effective elastic modulus (
E
) and strain-free partition coefficient (
D
0
). At each pressure,
E
values for the M1 and M2-sites increase with increasing Al concentration in the T-site
. For a given bulk composition,
E
values decrease with increased
T
. The decrease in
E
with increasing
T
accounts for the remarkable constancy of the degree of fractionation between chemically similar elements, e.g.
, over the range of pressures studied here.
for our experiments is found to be higher than predicted by the Hazen and Finger (
1979
) relationship between elastic moduli and interatomic distance. This is explained by deformation of the M1-site polyhedron leading to relative displacement and kinking of the clinopyroxene T-site chains. We developed expressions for
,
,
D
Sc
and
D
Ti
as functions of
P
,
T
and composition. We show the feasibility of using calculated
D
Ti
values in the prediction of
D
Zr
and
D
Hf
. Scandium and Ti partition coefficients were modelled based on the thermodynamic description for the crystal–melt exchange reaction and in terms of the energetics of the different charge-imbalanced configurations produced by insertion of a heterovalent trace cation. The resulting equations produce values of
D
Sc
and
D
Ti
that are within a factor of 2 of other experimentally determined values. Fits of the equations along the lherzolite solidus show that
D
Sc
remains compatible in clinopyroxene at high pressure and that ratios of Zr/Hf and Ti/Eu should vary subtly with the pressure at which melting occurred.
Publisher
Springer-Verlag,Springer Nature B.V
Subject
